Kai-Chi Chang et. al
Supplementary Data
Highly selective fluorescence sensing of Cu2+ ion by an arylisoxazole modified
calix[4]arene
Kai-Chi Chang, Li-Yang Luo, Eric Wei-Guang Diau, and Wen-Sheng Chung*
Department of Applied Chemistry, National Chiao-TungUniversity, Hsinchu, 30050,
Taiwan-ROC.
Table of contents
Content
Page No
S2.
1
H and 13C NMR Spectra of 1.
S3.
1
S4.
1
S5.
UV/vis spectra of 1 and 2 (20 µM) in CH3CN/CHCl3 (v/v = 1000:4) (Figure S7) &
H and 13C NMR Spectra of 2.
H and 13C NMR Spectra of 4.
Changes in fluorescence emission spectra of 2 (20 µM) before and after adding
200 µM concentration of various metal perchlorates in CH3CN/CHCl3 (v/v =
1000:4) (Figure S8).
S6
UV/vis spectra of 1 (20 µM) before and after adding a 200 µM concentration of
Cu(ClO4)2 in CH3CN/CHCl3 (v/v = 1000:4) (Figure S9) & Fluorescence emission
spectra of 1 (20 µM) upon addition of various equiv of Cu(ClO4)2 in DMSO
(Figure S10).
S7.
Fluorescence emission spectra of 1 (20 µM) upon addition of various equiv of
Cu(ClO4)2 in MeOH/CHCl3 (v/v = 1000:4). (Figure S11) & Stern-Volmer plot of 1
with Cu(ClO4)2 (Figure S12).
S8.
1
H NMR spectra of 2 (5.0 mM) in CDCl3/CD3CN (3/1) (a) and in the presence of
25 mM (5.0 equiv) of Cu(ClO4)2 (b), where * denotes an external standard CHCl3
(Figure S13) & Changes in fluorescence emission spectra of 1 (20 µM) before and
after adding 200 µM concentration of [(CH3CN)4Cu]PF6 (dash curve) and
Cu(ClO4)2 (short-dash curve) in CH3CN/CHCl3 (v/v = 1000:4) (Figure S14).
S9.
Fluorescence emission changes for the 1 (20 µM) with 3 equiv of Cu(ClO4)2 in
CH3CN/CHCl3 (v/v = 1000:4) upon addition of various amounts of
[(CH3CN)4Cu]PF6 (Figure S15).
S-1
1.0693
1.4298
1.0693
1.4298
3.5124
3.4684
4.4350
4.3913
5.3358
6.5544
6.9441
6.9084
7.8408
7.8118
7.5658
7.5436
7.5153
7.4457
7.4199
7.3955
7.2598
7.2171
8.5018
8.4726
8.5018
8.4726
7.8408
7.8118
7.5658
7.5436
7.5153
7.4457
7.4199
7.3955
7.2598
7.2171
6.9441
6.9084
6.5544
Kai-Chi Chang et. al
O
OH OH
O
N
8.6
8.4
8.2
8.0
7.8
7.6
7.4
7.2
7.0
6.8
6.6
1.4
ppm
1.2
O
N
ppm
Cl
Cl
1
Current Data Parameters
NAME
catch080905
EXPNO
1
PROCNO
1
F2 - Acquisition Parameters
Date_
20050808
Time
12.34
INSTRUM
spect
PROBHD
5 mm BBO
PULPROG
zg30
TD
16384
SOLVENT
CDCl3
NS
16
DS
0
SWH
4496.403 Hz
FIDRES
0.274439 Hz
AQ
1.8219508 sec
RG
35.9
DW
111.200 usec
DE
6.50 usec
TE
300.0 K
D1
1.50000000 sec
Figure S1.
1
3
H NMR (300 MHz) Spectrum of 1 in CDCl3.
Figure S2. 13C NMR (75.4 MHz) spectrum of 1 in CDCl3.
S-2
2
1
19.8744
4
20.8249
5
4.3869
6
4.3119
7
4.1523
8
2.0000
9
4.3031
4.7629
4.3953
4.3956
6.5393
10
4.2703
11
ppm
============ CHANNEL f1 =============
NUC1
1H
P1
10.00 usec
PL1
-3.00 dB
SFO1
300.1319508 MHz
F2 - Processing parameters
SI
16384
SF
300.1300063 MHz
WDW
EM
SSB
0
LB
0.10 Hz
GB
0
PC
1.00
O
1.3209
1.5892
2.3953
5.1321
7.6623
7.6398
7.6115
7.5481
7.5219
7.4974
7.8964
7.8673
8.6201
8.5908
8.6201
8.5908
7.8964
7.8673
7.6623
7.6398
7.6115
7.5481
7.5219
7.4974
7.2597
7.0891
6.6248
Kai-Chi Chang et. al
O
O
N
8.7
8.6
8.5
8.4
8.3
8.2
8.1
8.0
7.9
7.8
7.7
7.6
7.5
ppm
Cl
2
Current Data Parameters
NAME
catch011206
EXPNO
1
PROCNO
1
F2 - Acquisition Parameters
Date_
20060113
Time
5.44
INSTRUM
spect
PROBHD
5 mm BBO
PULPROG
zg30
TD
16384
SOLVENT
CDCl3
NS
16
DS
0
SWH
4496.403 Hz
FIDRES
0.274439 Hz
AQ
1.8219508 sec
RG
143.7
DW
111.200 usec
DE
6.50 usec
TE
300.0 K
D1
1.50000000 sec
4
3
2
Figure S3. 1H NMR (300 MHz) spectrum of 2 in CDCl3.
Figure S4. 13C NMR (75.4 MHz) spectrum of 2 in CDCl3..
S-3
1
9.7691
5
6.3759
6
2.1333
7
1.0026
8
2.0822
9
2.0713
2.1475
2.1386
10
2.1333
11
ppm
============ CHANNEL f1 =============
NUC1
1H
P1
9.90 usec
PL1
-3.00 dB
SFO1
300.1319508 MHz
F2 - Processing parameters
SI
16384
SF
300.1300057 MHz
WDW
EM
SSB
0
LB
0.10 Hz
GB
0
PC
1.00
1.3232
2.5373
2.5304
2.3518
2.5373
2.5304
4.5079
4.5009
4.5079
4.5009
7.0467
Kai-Chi Chang et. al
O
4.5
2.55
ppm
2.50
ppm
4
Current Data Parameters
NAME
catch031206
EXPNO
1
PROCNO
1
F2 - Acquisition Parameters
Date_
20060311
Time
17.33
INSTRUM
spect
PROBHD
5 mm BBO
PULPROG
zg30
TD
16384
SOLVENT
CDCl3
NS
16
DS
0
SWH
4496.403 Hz
FIDRES
0.274439 Hz
AQ
1.8219508 sec
RG
57
DW
111.200 usec
DE
6.50 usec
TE
300.0 K
D1
1.50000000 sec
7
6
5
4
3
2
Figure S5. 1H NMR (300 MHz) spectrum of 4 in CDCl3.
Figure S6.
13
C NMR (75.4 MHz) spectrum of 4 in CDCl3.
S-4
1
10.4843
8
1.0000
6.7719
9
2.2472
10
2.1994
11
ppm
============ CHANNEL f1 =============
NUC1
1H
P1
9.90 usec
PL1
-3.00 dB
SFO1
300.1319508 MHz
F2 - Processing parameters
SI
16384
SF
300.1300063 MHz
WDW
EM
SSB
0
LB
0.10 Hz
GB
0
PC
1.00
Kai-Chi Chang et. al
Absorbance
0.4
375
0.2
396
357
338
2
1
0.0
300
400
500
600
Wavelength (nm)
Figure S7. UV/vis spectra of 1 and 2 (20 µM) in CH3CN/CHCl3 (v/v = 1000:4).
Fluorescence Intensity (a.u.)
7
427
6
+
+
+
2+
2 and 2 + Li , Na , K , Mg ,
2+
2+
3+
2+
2+
Ca , Ba , Cr , Pb , Cu ,
2+
2+
2+
2+
2+
Hg , Cd , Ag , Ni , Mn ,
2+
and Zn ions, respectively.
5
4
3
2
1
0
400
450
500
550
600
Wavelength (nm)
Figure S8. Changes in fluorescence emission spectra of 2 (20 µM) before and after adding 200
µM concentration of various metal perchlorates in CH3CN/CHCl3 (v/v = 1000:4).
S-5
Kai-Chi Chang et. al
1 + Cu
Absorbance
0.4
2+
1
0.2
0.0
300
400
500
600
Wavelength (nm)
Fluorescence Intensity (a.u.)
Figure S9. UV/vis spectra of 1 (20 µM) before and after adding a 200 µM concentration of
Cu(ClO4)2 in CH3CN/CHCl3 (v/v = 1000:4).
7
435
6
5
1
1 + 100 equiv Cu
4
2+
1 + 200 equiv Cu
3
2+
2+
1 + 500 equiv Cu
2
1
0
400
450
500
550
600
650
Wavelength (nm)
Figure S10. Fluorescence emission spectra of 1 (20 µM) upon addition of various equiv of
Cu(ClO4)2 in DMSO.
S-6
Kai-Chi Chang et. al
Fluorescence Intensity (a.u.)
7
432
6
1
5
1 + 100 equiv Cu
2+
2+
1 + 200 equiv Cu
4
2+
1 + 500 equiv Cu
3
2
1
0
400
450
500
550
600
650
Wavelength (nm)
Figure S11. Fluorescence emission spectra of 1 (20 µM) upon addition of various equiv of
Cu(ClO4)2 in MeOH/CHCl3 (v/v = 1000:4).
3
I0/I
2
4
1
0
0.00000
Y = 1.58 * 10 * X + 1.01
2
R = 0.999
0.00005
2+
[Cu ]
Figure S12. Stern-Volmer plot of 1 with Cu(ClO4)2.
S-7
0.00010
0.00015
Kai-Chi Chang et. al
•
(b)
a
j
g i h
e
*
f
a
•
(a)
j
g
f
e
a
*
i h
O
e
O
N
f
g
h
Cl
j
8.5
8.0
7.5
7.0
6.5
6.0
5.5
ppm
i
2
Fluorescence Intensity (a.u.)
Figure 13. 1H NMR spectra of 2 (5.0 mM) in CDCl3/CD3CN (3/1) (a) and in the presence of 25
mM (5.0 equiv) of Cu(ClO4)2 (b), where * denotes an external standard CHCl3.
7
430
6
1
+
1 + Cu
2+
1 + Cu
1
+
1 + Cu
5
4
3
1 + Cu
2
2+
1
0
400
450
500
550
600
650
Wavelength (nm)
Figure S14. Changes in fluorescence emission spectra of 1 (20 µM) before and after adding 200
µM concentration of [(CH3CN)4Cu]PF6 (dash blue curve) and Cu(ClO4)2 (short-dash curve) in
CH3CN/CHCl3 (v/v = 1000:4).
S-8
Fluorescence Intensity (a.u.)
Kai-Chi Chang et. al
7
430
+
1, 1 + 3 eq. Cu , 1 + 30 eq. Cu
6
+
2+
1 + 3 eq. Cu ,
2+
+
1 + 3 eq. Cu + 3eq. Cu ,
2+
+
1 + 3 eq. Cu + 5eq. Cu
5
4
2+
+
1 + 3 eq. Cu + 10eq. Cu
2+
+
1 + 3 eq. Cu + 20eq. Cu
2+
+
1 + 3 eq. Cu + 30eq. Cu
3
2
1
0
400
450
500
550
600
650
Wavelength (nm)
Figure S15. Fluorescence emission changes for the 1 (20 µM) with 3 equiv of Cu(ClO4)2 in
CH3CN/CHCl3 (v/v = 1000:4) upon addition of various amounts of [(CH3CN)4Cu]PF6.
S-9