Electronic Supplementary Informations
for
Solvent viscosity tuned highly selective NIR and ratiometric fluorescent
sensing of Fe3+
by a symmetric chalcone analogue
Uzra Diwan, Ajit Kumar, Virendra Kumar and K.K.Upadhyay*
Department of Chemistry (Centre for Advanced Study), Faculty of Science, Banaras Hindu
University, Varanasi-221005, India
*E-mail: [email protected], Tel: +91 542 670 2488 ___________________________________________________________________________
EXPERIMENTAL
1.1 Apparatus:
The IR Spectra for the receptors 1 was recorded on JASCO-FTIR Spectrophotometer
while 1H NMR and
13C NMR spectra for the same were recorded on a JEOL AL 300 FT
NMR Spectrometer. Mass spectrometric analysis was carried out on a MDS Sciex API 2000
LCMS/Brukar Compass data analysis spectrometer. Electronic spectra were recorded at room
temperature (298 K) on a UV-1700 pharmaspec spectrophotometer with quartz cuvette (path
length=1 cm). Emission spectra were recorded on JY HORIBA Fluorescence
spectrophotometer.
1.2 Materials:
All reagents for synthesis were purchased from Sigma-Aldrich and were used without
further purification.
1.3 General Methods:
All titration experiments were carried at room temperature. All the cations were used
as their chloride. The 1H NMR spectra were recorded by using tetramethylsilane (TMS) as an
internal reference standard.. .
1.4. Theoretical studies:
All DFT calculations were carried out with the Gaussian 03 program. The structures
of receptor 1 in the absence and presence of anions were fully optimized in gaseous phase
using B3LYP functional with the 6-31g** basis set. To visualize the optimized structures
Gauss View software was used.
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Figure S1: 1HNMR spectrum of receptor 1
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Figure S2: 13
C NMR spectrum of receptor 1
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Figure S3: IR spectrum of receptor 1
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Figure S4: Mass spectrum of receptor 1
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Figure S5: Absorbance of receptor 1 in different solvent at 1×10-5
M
concentration
360 450 540
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Ab
so
rba
nc
e
Wavelength, nm
Diethylether
Acetone
ACN
DCM
Ethyl acetate
CHCl3
MeOH
DMF
EtOH
DMSO
Water
Ethelene glycol
Toluene
Hexane
Table 1: UV-visible absorption band of receptor 1 in various solvents and
corresponding absorbance
S. No Solvent Wavelength, nm Absorbance
1. ACN 423 nm 0.64
2. CHCl3 430 nm 0.94
3. CH2Cl2 430 nm 0.98
4. Diethyl ether 409 nm 0.74
5. MeOH 435 nm 0.89
6. EtOH 436 nm 0.73
7. Acetone 424 nm 1.04
8. DMF 434 nm 0.76
9. DMSO 439 nm 0.87
10. Water 435 nm 0.86
11. Ethyl acetate 415 nm 0.75
12. Ethylene glycol 445 nm 0.18
13. Hexane 397, 426 nm 0.58, 0.38
12. Toluene 410 nm 0.85
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Figure S6: Colour changes of receptor 1 upon respective additions of Cu2+
,
from left to right; receptor 1, 1+10 equiv. Cu2+
and 1+5 equiv. of Cu2+
Figure S7: Family of absorbance spectra of receptor 1 upon concomitant
additions of Fe2+
ion and its corresponding color changes
300 400 500 600 700 800 900
0.00
0.13
0.26
0.39
0.52
0.65
Ab
so
rba
nc
e
Wavelength, nm
621 nm
430 nm
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FIGURE S8: Job’s Plot of Fe3+
with receptor 1 showing 1:1 stoichiometry
0.0 0.2 0.4 0.6 0.8 1.0
0.00
0.05
0.10
0.15
0.20
0.25A
bs
orb
an
ce
at
68
0 n
m
[G]/[H]+[G]
Figure S9: Job’s Plot of Cu2+
with receptor 1 showing 1:2 stoichiometries
-0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
0.00
0.15
0.30
0.45
0.60
0.75
Ab
so
rba
nc
e a
t 4
60
nm
[H]/[H]+[G]
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Figure S10: Mass spectrum of 1+Fe3+
complex
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Figure S11: Mass spectrum of 1+Cu2+
complex
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Figure S12: (a) Colour changes of receptor 1 upon addition of 5 equivalent
various metal ions,
Figure S12: (b) Effect of various metal ions on the colour of 1+Fe3+
complex, from left to right; receptor 1, Fe3+
, Cr3+
, Mn2+
, Co2+
, Ni2+
, Cu2+
,
Zn2+
, Cd2+
, Hg2+
and Al3+
Figure S12: (c) Effect of various metal ions on the UV-visible spectra of
1+Fe3+
complex, from left to right; receptor 1, Fe3+
, Cr3+
, Mn2+
, Co2+
, Ni2+
,
Cu2+
, Zn2+
, Cd2+
, Hg2+
and Al3+
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300 600 900
0.0
0.5
1.0
1.5
2.0
Ab
so
rba
nc
e
Wavelength/nm
Figure S13: Non-linear fit plot of receptor 1with Fe3+
0.00000 0.00002 0.00004 0.00006 0.00008 0.00010
0.00
0.04
0.08
0.12
0.16
Ab
so
rba
nc
e a
t 9
65
nm
[Fe3+
]
Figure S14: Determination of detection limit and calibration curves of
receptor with Fe3+
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Figure S15: Emission responses of receptor 1 in different solvents:
450 500 550 600 650 700
0.00
3.50x106
7.00x106
1.05x107
1.40x107
Inte
ns
ity
/a.u
.
Wavelength/nm
EtOH
CHCl3
CH2Cl2
Hexane
Ethylacetate
Acetone
ACN
DMF
MeOH
DMSO
THF
Ether
Isopropanol
Toluene
y = 43193x + 0.0026 R² = 0.9971
LOD=5.8E-08
0.4
0.6
0.8
1
1.2
1.4
1.00E-05 1.50E-05 2.00E-05 2.50E-05 3.00E-05
Absorban
ce
Concentration/µm
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Figure S16: Non-linear fit plots of receptor 1 obtained from fluorescence
titration data between receptor 1 and Fe3+
0.000000 0.000002 0.000004 0.000006 0.000008 0.000010
2.0x106
4.0x106
6.0x106
8.0x106
1.0x107
1.2x107
1.4x107
1.6x107
1.8x107
2.0x107
Inte
ns
ity
at
53
8 n
m
[Fe3+
]
Figure S17: Determination detection limit and calibration curves of
receptor 1 with Fe3+
through fluorescence data
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