A new series of dinucleating macrocyclic ligands and their complexes of zinc(II) |
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Authors: | Ze-Li Yuan Qi-Long Zhang Xue Liang Bi-Xue Zhu Leonard F. Lindoy Gang Wei |
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Affiliation: | 1. Department of Chemistry, Guizhou University, Guizhou 550025, PR China;2. Centre for Heavy Metal Research, School of Chemistry, The University of Sydney, NSW 2006, Australia;3. CSIRO Materials Science and Engineering, P.O. Box 218, Lindfield, NSW 2070, Australia |
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Abstract: | A new category of dinucleating macrocyclic Schiff base ligands with ring sizes from 34- to 52-membered have been synthesised employing metal template procedures involving the reaction of o-phenylenediamine with a series of α,ω-bis(3′-hydroxy-4′-formylphenyloxy)alkanes in the presence of calcium(II), barium(II) or manganese(II). The latter cations act as ‘transient’ templates for formation of the corresponding metal-free Schiff base macrocyclic ligands, H4Ln (where n signifies the number of carbons in each linking bis-alkoxy chain); the macrocycles corresponding to n = 4, 6 and 8 were isolated and characterised while, for n = 1, in which single methylene groups acts as the bridges between salicyl moieties, the cyclic product was used directly for preparation of its dinuclear complex, [Zn2L1], without prior isolation. Evidence for the templating role of barium in the preparation of H4L6 and H4L8 was obtained by isolation of the corresponding species of type H4Ln·2Ba(ClO4)2 (n = 6 or 8) as ‘intermediates’ before generation of the respective metal-free macrocycles. Reaction of zinc(II) acetate with the free macrocycles in methanol yielded complexes of type [Zn2Ln] in all cases. A related non-cyclic ligand, H2L0 and its corresponding mononuclear complex, [ZnL0]·H2O, were also synthesised and its spectral properties compared with those of the macrocyclic derivatives. The elemental analyses, 1H NMR, IR, UV–Vis and MS spectra of the respective zinc complexes in each case were in accord with the formation of the expected 2:2 condensation product. The results of DFT calculations to probe aspects of the electronic and structural natures of both H2L1 and H4L4 are briefly presented. |
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Keywords: | Zinc(II) Dinucleating macrocycles Template synthesis Schiff base |
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