Supplementary data (Figures)
Synthesis and characterization of M(II) (M = Cd, Hg and Pb) complexes with
naphthodiaza-crown macrocyclic ligand and study of metal ion recognition by
fluorescence, 1H NMR spectroscopy, and DFT calculation
BAHRAM GHANBARI* and MORTEZA ZAREPOUR-JEVINANI
Figure S1. The fluorescence spectra of L (1×10-6 M) in the presence of nitrate salt of the
metal ions (1×10-6 M): 1. Hg(II), 2. Zn(II), 3. Cd(II), 4. Al(III), 5. Ni(II), 6. Cs(I), 7. no
cation(only L), 8. Mg(II), 9. Na(I), 10. Fe(II), 11. Pb(II), 12. Cu(II), 13. Co(II), 14. K(I), 15.
Cr(III), 16. Ca(II), 17. Ba(II), 18. Mn(II) (1×10-6 M) at 298 K (excitation = 280 nm, emission =
358 nm, excitation and emission slit widths = 5.0 nm).
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Figure S2. The FEF as enhancement and/or quenching of the emission band observed for the
interaction of L (1×10-6 M) with the library metal cation nitrates (1×10-6 M) in ethanol at
298 K (excitation = 280 nm, emission = 358 nm, excitation and emission slit widths = 5.0 nm).
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Figure S3. The FEF of L (1×10-6 M) during the addition of Hg(II) cation along with each of
the library nitrate salt of the metal ions (1×10-6 M) in the solution of L at 298 K (excitation =
280 nm, emission = 358 nm, excitation and emission slit widths = 5.0 nm).
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Figure S4. The UV-visible spectral changes of L (1×10-4 M) in the presence of different
nitrate salt of the metal ions: 1. L (no cation), 2. Ba(II), 3. Pb(II), 4. Mn(II), 5. Fe(II), 6.
Cr(III), 7. K(I), 8. Ni(II), 9. Cu(II), 10. Zn(II), 11. Cd(II), 12. Co(II), 13. Ca(II), 14. Na(I), 15.
Cs(I), 16. Mg(II), 17. Al(III), and 18. Hg(II) (1×10-4 M) in ethanol at 298 K.
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Figure S5. UV-visible spectral changes of L (1×10-3 M) as a function of the various
concentrations Hg(II) nitrate (0–1.0 equiv.) (250-700 nm) in ethanol at 298 K. Inset: the
magnified absorption changes related to the amounts of Hg(II) added (400-650 nm).
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Figure S6. The color changes of L in the presence of the library metal ion nitrates.
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Figure S7. The Job’s plots for Hg(II)/L interaction derived from the fluorescent emission of
emission = 358 nm in ethanol.
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Figure S8. The BH plots derived from the fluorescence emission band at emission = 358 nm
observed for Hg(II)/L interaction in ethanol at three different temperatures: 298 K (▲),
308 K (■), and 318 K (●).
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Figure S9. The BH plot derived from the absorbance band at UV = 280 nm observed for
Hg(II)/L complex formation in ethanol at 298 K.
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Figure S10. The EI mass spectra of M(II)/L complexes; from top to bottom M were Cd, Hg,
and Pb.
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Figure S11. 1H NMR spectrum of L (down) and [Hg(II)L]2+ (top) in DMSO-d6 at 298 K.
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Figure S12. 1H NMR spectrum of L (down) and [Cd(II)L]2+ (top) in DMSO-d6 at 298 K.
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Figure S13. 1H NMR spectrum of L (down) and [Pb(II)L]2+ (top) in DMSO-d6 at 298 K.
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Figure S14. The effect of the ionic size of the cation on Hx chemical shifts of L in [M(II)L]2+
(Cd, Hg, and Pb) complexes.
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Figure S15. The relation between FEF and the cation size for the complexes of the library
metal ions with L.
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