A facile ratiometric and colorimetric azo-dye possessing
chemosensor for Ni2+ and AcO- detection
Gargi Dhaka, Navneet Kaur and Jasvinder Singh
Department of Chemistry, Panjab University, Chandigarh 160014, India
General methods and materials
All of the solvents and reagents were commercially available and of analytical reagent grade.
Infrared (IR) data were collected on a Thermo scientific Nicolet model iS50 FT-IR
spectrophotometer. 1H NMR and 13C NMR spectra were collected on a Bruker 400/Jeol 300
spectrometer at 400 MHz. 1H chemical shifts are reported in parts per million (ppm) downfield
from TMS as an internal standard. Ultraviolet-visible (UV-vis) spectra were recorded using a
Jasco V-530 UV-vis spectrophotometer.
General procedure for UV-vis experiments
Stock solution of the chemosensor 1 (1 x 10-3 M) was prepared in DMSO. This stock solution
was diluted with THF-H2O (9:1, v/v) and used further for different spectroscopic experiments.
All the metal ions such as Na+, K+, Mg2+, Mn2+, Fe2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Hg2+ and Cd2+
were added as their perchlorate salts whereas all the anions such as F -, Cl-, Br-, I-, AcO-, H2PO4-,
HSO4- and SO42- were added as their tetrabutylammonium salts for the different UV-vis
experiments.
General procedure for 1H NMR experiments
For 1H NMR titrations, three stock solutions were prepared in DMSO-d6 (4.3 x10-2 M), one of
them containing host only and other two containing an appropriate concentration of guest.
Aliquots of the two solutions were mixed directly in NMR tubes, which then was diluted to 0.5
mL with DMSO-d6 if need be.
 Corresponding author. Tel.: +91 172 2534430; fax: +91 172 2545074; e-mail: neet_chem@yahoo.co.in;
neet_chem@pu.ac.in
AZOBTZ
12.3869
9.1285
9.1227
8.8654
8.8592
8.7309
8.7271
8.7192
8.7155
8.2180
8.2140
8.2128
8.2081
8.1977
8.1930
8.1917
8.1877
8.1786
8.1591
8.1287
8.1086
8.0470
8.0407
8.0250
8.0187
7.6365
7.6245
7.6162
7.6151
7.6044
7.6032
7.5906
7.5876
7.5724
7.5699
7.5524
7.5494
7.4918
7.4892
7.4716
7.4540
7.4515
7.3041
7.2821
3.3602
2.5091
2.5047
2.5002
2.4957
2.4914
BRUKER
AVANCE II 400 NMR
Spectrometer
SAIF
Panjab University
Chandigarh
Current Data Parameters
NAME
Feb20-2015
EXPNO
90
PROCNO
1
F2 - Acquisition Parameters
Date_
20150220
Time
14.53
INSTRUM
spect
PROBHD
5 mm PABBO BBPULPROG
zg30
TD
65536
SOLVENT
DMSO
NS
8
DS
2
SWH
12019.230 Hz
FIDRES
0.183399 Hz
AQ
2.7263477 sec
RG
322
DW
41.600 usec
DE
6.00 usec
TE
297.1 K
D1
1.00000000 sec
TD0
1
======== CHANNEL f1 ========
NUC1
1H
P1
10.90 usec
PL1
-3.00 dB
SFO1
400.1324710 MHz
F2 - Processing parameters
SI
32768
SF
400.1300033 MHz
WDW
EM
SSB
0
LB
0.30 Hz
GB
0
PC
1.00
14
13
12
11
10
9
8
7
6
5
4
3
2
1
0
ppm
1
Fig. S1: H NMR of chemosensor 1.
avtar_saifpu@yahoo.co.in
Fig. S2: HRMS of chemosensor 1.
319 nm
Absorbance
0.4
339 nm
0.3
0.2
0.1
0
1
Na
K
Mg
Al
Mn
Ni
Co
Cu
Zn
Cd
Metal ions (Mn+)
Fig. S3: The UV-vis absorption spectrum of 1 (10 µM) in the presence of 500 equiv. of metal
ions in 9:1 (v/v) aqueous THF (pH 7.0 HEPES buffer).
7.0
6.5
1/[A-Ao]
6.0
5.5
5.0
4.5
400
600
800
1000 1200 1400 1600 1800 2000 2200 2400
2+
1/[Ni ]
Fig. S4: Plot of 1/(A-A0) versus 1/[Ni2+] showing a linear relationship
415 nm
0.5
Absorbance
0.4
0.3
0.2
Cu2+
0 - 42 equiv.
0.1
0
240
340
440
540
640
Wavelength (nm)
Fig. S5: The UV-vis absorption titration curve of 1 with Cu2+ in 9:1 (v/v) aqueous THF (pH 7.0
HEPES buffer); Inset: Binding isotherm of 1 with Cu2+ at wavelength 415 nm.
319 nm
0.5
Absorbance
0.4
339 nm
0.3
415 nm
0.2
0.1
0
240
340
440
540
640
Wavelength (nm)
Fig. S6: The UV-vis absorption titration curve of 1 with Co2+ in 9:1 (v/v) aqueous THF (pH 7.0
HEPES buffer); Inset: Binding isotherm of 1 with Co2+ at wavelengths 319 and 415 nm.
Absorbance
475
319
0.4
339
0.2
0
339
319
475
Anions (An-)
Fig. S7: The UV-vis absorption spectrum of 1 (10 µM) in the presence of 500 equiv. of anions in
9:1 (v/v) aqueous THF (pH 7.0 HEPES buffer).
475 nm
0.5
319 nm 339 nm
CN-
Absorbance
0.4
0.3
0.2
0.1
0
240
340
440
540
640
740
Wavelength (nm)
Fig. S8: The UV-vis absorption titration curve of 1 with CN- in 9:1 (v/v) aqueous THF (pH 7.0
HEPES buffer); Inset: Binding isotherm of 1 with CN- at wavelengths 319, 339 and 475 nm.
Absorbance
0.4
319 nm
339 nm
0.3
0.2
475 nm
0.1
0
240
340
440
540
640
740
Wavelength (nm)
Fig. S9: The UV-vis absorption titration curve of 1 with F- in 9:1 (v/v) aqueous THF (pH 7.0
HEPES buffer); Inset: Binding isotherm of 1 with F- at wavelengths 319, 339 and 475 nm.