Abstract
The selectivity, anion uptake and exchangeability of anion-binding by metal salt extractants of the form [M2 L 2]4+ have been assessed by the method of anion exchange chromatography in biphasic systems. The order of sulfate-, nitrate-, and chloride-uptake into the solid copper(II) complex as of the dioxime pro-ligand N,N′-dimethyl-N,N′-hexamethylenedi(3-hydroxyiminomethyl-2-hydroxy-5-tert-butylbenzylamine (L 1) is 56, 42, and 16%, respectively, consistent with the relative magnitudes of formation constants for the inclusion complexes, [A⊂Cu2 L 1 2]n+ where A = anion, found in UV–vis titration studies in a single phase. X-ray structural determination of the bis-benzylimine pro-ligand, N,N′-dimethyl-N,N′-hexamethylenedi-(3-benzyliminomehyl-2-hydroxy-5-tert-butylbenzylamine), nickel(II) sulfato complex [SO4⊂Ni2 L 2 2]SO4 reveals the nickel atoms to have a significant tetrahedral distortion, providing more favourable sulfate-alkylammonium interactions within the cage.
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Notes
Sample volume = 25 µL, Initial concentrations: SO4 (101.806 ppm), NO3 (127.969 ppm), Cl (74.192 ppm), m(SO4) = 101.806 mg/L * 25e−6 L = 2.545e−6 g, n(SO4) = 2.545e−6 g/96.064 g/mol = 2.649e−8 mol, 55.9% uptake, so n(SO4) taken up = 1.481e−8 mol, m(NO3) = 127.969 mg/L * 25e−6 L = 3.199e−6 g, n(NO3) = 3.199e−6/62.01 g/mol = 5.159e−8 mol, 42.3% uptake, so n(NO3) taken up = 2.182e−8 mol, m(Cl) = 74.192 mg/L * 25e−6 L = 1.855e−6 g, n(Cl) = 1.855e−6 g/35.453 g/mol = 5.232e−8 mol, 15.9% uptake, so n(Cl) taken up = 0.832e−8 mol, n(SO4):n(NO3 + Cl) = 1.481e−8 mol:3.014e−8 mol = 1:2.
1% HCO3 −/CO 2−3 buffer solution prepared from the eluent concentrate supplied by Dionex (P/N 063965).
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Chang, J.YC., Parsons, S., Plieger, P.G. et al. Anion-selective receptors based on dinuclear copper(II) and nickel(II) cage complexes of bis-salicylaldimines. J Incl Phenom Macrocycl Chem 71, 529–536 (2011). https://doi.org/10.1007/s10847-011-0011-x
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DOI: https://doi.org/10.1007/s10847-011-0011-x