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Azocalixarenes. 6: Synthesis, complexation, extraction and thermal behaviour of four new azocalix[4]arenes

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Abstract

Four new azocalix[4]arenes {5,11,17,23-tetrakis[(2-hydroxy-5-tert-butylphenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (1), 5,11,17,23-tetrakis[(2-hydroxy-5-nitro phenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (2), 5,11,17,23-tetrakis[(2-amino-5-carboxylphenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (3) and 5,11,17,23-tetrakis[(1-amino-2-hydroxy-4-sulfonicacidnapthylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (4)} have been synthesized from p-tert-butylphenol, p-nitrophenol, p-aminobenzoic acid and 1-amino-2-hydroxy-4-sulphonic acid by diazo coupling reaction with p-aminocalix[4]arene. The resulting ligands (1–4) were treated with three transition metal salts (e.g., CuCl2·2H2O, NiCl2·6H2O or CoCl2·6H2O). Cu(II), Ni(II) and Co(II) complexes of the azocalix[4]arene derivatives were obtained and characterized by UV-vis, IR, 1H-NMR spectroscopic techniques and elemental analysis. All the complexes have a metal:ligand ratio of 2:1. The Cu(II) and Ni(II) complexes of azocalix[4]arenes are square-planar, while the Co(II) complexes of azocalix[4]arenes are octahedral with water molecules as axial ligands. The solvent extraction of various transition metal cations from the aqueous phase to the organic phase was carried out by using azocalix[4]arenes (1–4). It was found that, azocalix[4]arenes 1, 2 and 3 examined selectivity for transition metal cations such as Ag+, Hg+ and Hg2+. In addition, the thermal stability of metal:azocalix[4]arene complexes were also reported.

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Scheme 1
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Scheme 2
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  1. Department of Chemistry, Faculty of Science-Arts, Pamukkale University, 20017, Denizli, Turkey

    Mine Sulak Ak & Hasalettin Deligöz

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  1. Mine Sulak Ak
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  2. Hasalettin Deligöz
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Correspondence to Hasalettin Deligöz.

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Dedicated to Prof. Dr. Mustafa Yılmaz on the occasion of his 50th birthday

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Ak, M.S., Deligöz, H. Azocalixarenes. 6: Synthesis, complexation, extraction and thermal behaviour of four new azocalix[4]arenes. J Incl Phenom Macrocycl Chem 59, 115–123 (2007). https://doi.org/10.1007/s10847-007-9300-9

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