electronic supplementary informations for · nmr spectrometer. mass spectrometric analysis was...

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.

Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2013

Electronic supplementary Informations

P a g e | 2

Figure S1: 1HNMR spectrum of receptor 1



P a g e | 3

Figure S2: 13

C NMR spectrum of receptor 1



P a g e | 4

Figure S3: IR spectrum of receptor 1



P a g e | 5

Figure S4: Mass spectrum of receptor 1



P a g e | 6

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



P a g e | 7

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



P a g e | 8

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]



P a g e | 9

Figure S10: Mass spectrum of 1+Fe3+

complex



P a g e | 10

Figure S11: Mass spectrum of 1+Cu2+

complex



P a g e | 11

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+



P a g e | 12

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+



P a g e | 13

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



P a g e | 14

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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