Supporting Information

New sensitive and selective calixarene based fluorescent sensors for the detection of Cs+ in an organoaqueous medium

Naresh Kumar,a Qui Pham-Xuan,a Alexis Depauw,a Miryana Hemadi,b Nguyet-Thanh Ha-Duong,b Jean-Pierre Lefevre,a Minh-Huong Ha-Thi*ac and Isabelle Leray*a

300 400 500 600

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0.02

0.04

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Abso

rban

ce

(nm)

Ligand Ligand+Cs+

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0.0

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I F (a.

u.)

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Ligand + Cs+

Ligand

Figure S1. Absorption (a) and emission (b) spectra of Calix-COU-Benz (2.1 x 10-6 M) upon addition of a large excess of cesium acetate (9mM) in CH3CN/H2O (8/2; v/v). (λexc = 397 nm).

Figure S2: Calculated charges of oxygen atoms on optimized structures of the simplified calixarene and its Cs+ complex. Calculations were performed with the Gaussian software. All calculations were performed using the B3LYP/6-31G and the B3LYP/LANL2DZ method.1 Total energy are -2609.43 and -2629.24 a.u. for the ligand

and the Cs+ complex, respectively. A decrease of the charge on oxygen atoms on the 6 and 7 positions of the coumarin were observed on the Cs+ complex.

Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017

Water HEPES pH = 70.7

0.8

0.9

1

1.1

1.2

1.3

1.4Free ligand Ligand + Cs

Figure S3. Fluorescence response at 562 nm of Calix-COU-Benz-CN (3.1 x 10-6 M) in the presence of Cs+ 100 µM in CH3CN/H2O 8/2 and in CH3CN/HEPES buffer 10 mM (pH = 7) 8/2.

Wat

er

HEP

ES p

H =

7

Ca(

II) 2

mM

Li(I

) 2m

M

Na(

I) 2

mM

K(I

) 0.1

mM

K(I

) 0.5

mM

Ag(

I) 0

.1m

M

Zn(I

I) 0

.1m

M

Fe(I

I) 0

.03m

M0.7

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1

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1.4Competing cation Competing cation + Cs

Figure S4. Selectivity diagram of Calix-COU-Benz-CN (3.1 x 10-6 M) in the presence of selected competitive metal ions in CH3CN/H2O 8/2. [Cs+] = 100 µM, , λexc = 456 nm, λem = 562 nm

Ligand CsCl CsClO4 CsAc0.9

1

1.1

1.2

1.3

1.4

Figure S5. Fluorescence intensity at 562 nm of Calix-COU-Benz-CN (3.1 x 10-6 M) in CH3CN/H2O 8/2, in the presence of Cs+ 100 µM from various cesium salts.

Figure S6: 1H NMR Spectrum of 1 (DMSO-d6, 400 MHz).

Figure S7: 1H NMR Spectrum of COU-Benz (CDCl3, 400 MHz).

Figure S8: 13C NMR Spectrum of COU-Benz (CDCl3, 100 MHz).

Figure S9: Mass spectrum (HRMS: TOF MS ES+) of COU-Benz.

Figure S10: 1H NMR Spectrum of 2 (CDCl3, 400 MHz).

Figure S11: 13C NMR Spectrum of 2 (CDCl3, 100 MHz).

Figure S12: Mass spectrum (HRMS: TOF MS ES+) of 2.

Figure S13: 1H NMR Spectrum of Calix-COU-Benz (CDCl3, 400 MHz).

Figure S14: 13C NMR Spectrum of Calix-COU-Benz (CDCl3, 100 MHz).

Figure S15: Mass spectrum (HRMS: TOF MS ES+) of Calix-COU-Benz.

Figure S16: 1H NMR Spectrum of Calix-COU-Benz-CN (CDCl3, 400 MHz).

Figure S17: 13C NMR Spectrum of Calix-COU-Benz-CN (CDCl3, 100 MHz).

Figure S18: Mass Spectrum (HRMS: TOF MS ES+) of Calix-COU-Benz-CN.

Figure S19: 1H NMR Spectrum of COU-Benz-CN (DMSO-d6, 400 MHz).

Figure S20: 13C NMR spectrum of Benz-CN (DMSO-d6, 100 MHz).

Figure S21: Mass spectrum (HRMS: TOF MS ES+) of Benz-CN.

Reference

(1) Korovitch, A.; Mulon, J. B.; Souchon, V.; Lion, C.; Valeur, B.; Leray, I.; Ha-Duong, N. T.; Chahine, J. J. Phys. Chem. B 2009, 113, 14247.