Metal ion interaction of two new tritopic N2O13 macrobicycles with B15C5 moieties in acetonitrile solution

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The synthesis of two new tritopic crown ligands (L1 and L2) bearing two benzo-15-crown-5 lateral moieties linked through a dibenzo-trioxa chain together with their interaction with metal ions, in acetonitrile and acetonitrile-water (50%, v/v) solutions is reported. The influence of K+, Na +, Li+, Ca2+, Ba2+, Cu2+, Zn2+, Cd2+, Pb2+ and Al3+, on the spectroscopic properties of these diaza-polyoxa ligands was investigated by absorption spectrophotometry and in some cases by fluorescence emission spectroscopy. Coordination with alkaline (Na+, K+ and Li+) and alkaline earth (Ca2+and Ba2+) metal ions is assumed to be weak with both macrobicyclic ligands, while the interaction with both imine and amine derivatives causes a minor effect in the absorption spectra. Coordination with Cu2+, Zn2+ and Pb2+ in acetonitrile solution causes a major change in the absorption spectra of the chromophores. In the case of Cu2+, addition of the metal to L1 or L2 leads to a blue-violet complex in solution with an absorbance maximum centred at 590 nm. Interaction of the Schiff-base L1 with Pb 2+ leads to a short wavelength shift in the absorption bands, comparable with the ZnL1 complex. Presence of transition metal ions such as Co2+, Ni2+and Cd2+ do not remarkably affect the absorption spectra of L1 and L2 in solution. Trivalent aluminium has a modest effect in the absorption bands of both N2O13 donor set bismacrocyclic ligands. The fluorescence study of L2 in the presence of Na +, K+, Ca2+, Ba2+, Co2+, Cu2+, Ni2+, Pb2+ and Al3+shows that Cu2+, Pb2+ and Al3+ complexes form non-fluorescent complexes.

Original languageEnglish
Pages (from-to)249-258
Number of pages10
JournalJournal of Inclusion Phenomena
Issue number3-4
Publication statusPublished - 1 Dec 2004


  • Absorption spectra
  • Emission spectra
  • Macrobicyclic crown ligands
  • Metal complexes


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