Water-Soluble Bismuth(III) Polynuclear Tyrosinehydroximate Metallamacrocyclic Complex: Structural Parallels to Lanthanide Metallacrowns

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.

Design and synthesis of dinuclear bismuth(III) complexes with potent ribonuclease-like activity

“…To confirm the relevance of the bismuth(III) ion in the ribonuclease-like activity, we compared it to lanthanide(III) ions because they exhibit similar properties in terms of oxidation states, ionic radii, coordination numbers, and coordination geometry. 38,39 Furthermore, some lanthanide(III) complexes have been reported to cleave RNA-phosphodiester bonds. 14,16,40,41 Thus, Bi(OTf)3, La(OTf)3, or Eu(OTf)3 were mixed with L3 in DMSO to obtain the corresponding dinuclear complexes in situ, which were subsequently directly subjected to the AA(rA)AA cleavage assay.…”

The chemistry of the s- and p-block elements with 2,2′:6′,2′′-terpyridine ligands

“…339 Very high coordination numbers (up to 10) are typical for Bi III and point to the often discussed similarity with the trivalent lanthanide ions Ln III . 340 The solvothermal reaction of BiI 3 , Zn (NO 3 ) 2 •6H 2 O, and tpy in an EtOH/water mixture afforded the unusual complex [Bi(tpy) 2 I 2 ][Bi 2 I 7 (tpy)], in which the cation as well as the anion each represented a Bi III -tpy complex (Fig. 43c).…”