Abstract
Recently there has been a great deal of interest and associated research into aspects of the coordination chemistry of lanthanides and bismuth—elements that show intriguing common features. This work focuses on the synthesis and characterization of a novel bismuth(III) polynuclear metallamacrocyclic complex derived from aminohydroxamic acid, in order to compare the coordination ability of Bi3+ with the similarly sized La3+ ions. A polynuclear tyrosinehydroximate Bi(OH)[15-MCCu(II)Tyrha-5](NO3)2 (1) was obtained according to the synthetic routes previously described for water-soluble Ln(III)-Cu(II) 15-MC-5 metallacrowns. Correlations between structural parameters of Bi(III) and Ln(III) complexes were analyzed. DFT calculations confirmed the similarity between molecular structures of the model bismuth(III) and lanthanum(III) tyrosinehydroximate 15-metallacrowns-5. Analysis of the electronic structures revealed, however, stronger donor-acceptor interactions between the central ion and the metallamacrocycle in the case of the lanthanum analogue. Thermochromic properties of 1 were studied.
Highlights
Bismuth(III) complexes have received increased interest due to their high effectiveness in eradication of Helicobacter pylori, and as potential antimicrobial and anti-leishmanial agents [1,2,3].Up to now, many coordination bismuth(III) compounds with a large variety of ligands and coordination environments had been synthesized and explored in biomedical applications [4,5,6,7,8]
This study found that it is necessary to take into account that the coordination chemistry of bismuth can be influenced by a stereochemically active lone pair, and bismuth has much higher Pauling electronegativity (1.9) than that of lanthanides (1.10–1.25) [22]
To develop the generation of coordination Bi(III) complexes with biologically important ligands, we considered polynuclear aminohydroximate Ln(III)-Cu(II) complexes, which belong to a family of 15-MC-5 metallacrowns
Summary
Bismuth(III) complexes have received increased interest due to their high effectiveness in eradication of Helicobacter pylori, and as potential antimicrobial and anti-leishmanial agents [1,2,3]. Many coordination bismuth(III) compounds with a large variety of ligands and coordination environments had been synthesized and explored in biomedical applications [4,5,6,7,8]. The chemistry of Bi(III) explored in this purpose to date is rather scarce, and the study of bismuth complexes in aqueous solutions is often difficult. Within group 15, antimony and arsenic compounds are generally of high toxic nature, whereas those of bismuth exhibit a significantly reduced
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