A novel receptor for detection of Zn2+ metal ion and F¯, H2PO4¯ and AcO¯ anions in aqueous media: A DFT study

MasoumehOrojlooa, RaziyehArabahmadib,Mohammad Solimannejada, PeymanZolgharneincand SaeidAmania*

aChemistry Department, Faculty of Sciences, Arak University, Dr. Beheshti Ave.

Arak 38156-88349, Iran

bChemistry Department, Payame Noor University (PNU), Tehran 19395-3697, Iran

cMaterial Science and Engineering Department, The University of Sheffield, Sheffield, UK

*Corresponding author

E-mail: ; Phone office: +98 86 34173415; Fax office: +98 86 34173406

Contents:

Fig.S1Modified Benesi-Hildebrand plot for sensor Lwith Zn+2at 495 nm

Fig.S2 Job’s plot for sensor L with Zn+2 at 495 nm.

Fig. S3 MALDI-TOF Mass spectrum for Zn+2 complexes

Fig. S4: (a) FT-IR spectrum of sensor L, (b) FT-IR spectrum of Zn+2complex with L

Fig. S5 (a) 1HNMR spectrum of the free ligand (L) and (b) Zn+2complex in DMSO-d6

Fig.S6 Absorption spectra of L (5⤬10-5 mol.L-1) in DMSO in the presence of Zn+2 (10 equiv.) upon addition of EDTA solution (10 equiv.)

Fig. S7 Absorption spectra and color changes for competition experiment of receptor L (4⤬ 10-5 mol. L-1) towards Zn2+ in the presence of 10 equiv. of Cd2+ and Pb2+ cations in DMSO at 495 nm.

Fig.S8 (a, b) UV–Vis titration of L (4⤬10-5 mol.L-1) in DMSO with incremental addition of F¯ and AcO¯ anions as their TBA salts (0–2 equiv.). Insets showing the molar ratio plot (top) and job plot (bottom) at selected wavelength.

Fig. S9 Benesi–Hildebrand plot of L with (a) H2PO4¯,(b)F¯ and (c)AcO¯ at 510 nm.

Fig.S10 Color changes and UV–Vis titration of L (4⤬10-5 mol.L-1) in 9:1 DMSO/H2O with incremental addition of (a)NaH2PO4, (b)NaF and (c)NaAcO (0–2 equiv.) in water.

Fig. S11 Job plot of L with (a) H2PO4¯,(b)F¯ and (c)AcO¯ at 510 nm.

Fig. S12(a) Absorption spectrum of L on the addition of Zn2+ (2 equivalents) and (a)F¯ and (b)AcO¯ (c) H2PO4¯ simultaneously.

Fig. S13 Time evolution of receptor L in DMSO in the presence of 10 equiv. of H2PO4‾, AcO‾ and F‾‾ions

Fig. S14 1H NMR titration plot of sensor (L) with TBAF in DMSO-d6 (aliphatic region)

Fig. S151H NMR titration plot of sensor (L) in DMSO-d6 with NaAcO in D2O

Fig.S1Modified Benesi-Hildebrand plot for sensor L with Zn+2at 495 nm

Modified Benesi–Hildebrand equation

2D + A → [D2A]

([D]0)2/Abs= 4/ε + 1/εKf⤬ 1/[A]0

[D]0= is the concentration of donor

[A]0= is the concentration of acceptor (variant)

ε = is the molar extinction coefficients of the mixture

Abs = is the absorbance of the mixture

Ka= 1/ (ε ⤬ slope)


Fig.S2 Job’s plot for sensor L with Zn+2 at 495 nm.

Fig. S3MALDI-TOF Mass spectrum for Zn+2complexes

Fig. S4: (a) FT-IR spectrum of sensor L, (b)FT-IR spectrum of Zn+2complex with L

Fig.S5 (a)1HNMR spectrum of the free ligand (L) and (b) Zn+2complex in DMSO-d6

Fig.S6 Absorption spectra of L (5⤬10-5 mol.L-1) in DMSO in the presence of Zn+2 (10 equiv.) upon addition of EDTA solution (10 equiv.)

Fig.S7 Absorption spectra and color changes for competition experiment of receptor L (4⤬10-5 mol.L-1) towards Zn2+ in the presence of 10 equiv. of Cd2+ and Pb2+ cations in DMSO at 495 nm.

Fig.S8 (a, b) UV–Vis titration of L (4⤬10-5 mol.L-1) in DMSO with incremental addition of F¯ and AcO¯anions as their TBA salts(0–2 equiv.). Insets showing the molar ratio plot (top) and job plot (bottom) at selected wavelength.

Fig.S9Benesi–Hildebrand plot of L with (a) H2PO4¯,(b)F¯ and (c)AcO¯ at 510 nm.

Fig.S10Color changes and UV–Vis titration of L (4⤬10-5 mol.L-1) in 9:1 DMSO/H2O with incremental addition of (a)NaH2PO4, (b)NaF and (c)NaAcO(0–2 equiv.)in water.

Fig. S11 Job plot of L with (a) H2PO4¯,(b)F¯ and (c)AcO¯ at 510 nm.

Fig. S12(a) Absorption spectrum of L on the addition of Zn2+ (2 equivalents) and (a)F¯ and (b)AcO¯ (c) H2PO4¯ simultaneously.

Fig. S13 Time evolution of receptor L in DMSO in the presence of 10 equiv. of H2PO4‾, AcO‾ and F‾‾ions

Fig. S141H NMR titration plot of sensor (L) with TBAF in DMSO-d6(aliphatic region)

Fig. S151H NMR titration plot of sensor (L) in DMSO-d6 with NaAcO in D2O