Pillar[5]arene-based phosphine oxides: novel ionophores for solvent extraction separation of f-block elements from acidic media
A new class of pillar[5]arene-based phosphine oxides tethered with ten chelating groups on both rims of the pillar were synthesized viatwo steps from macrocyclization of 1,4-bis(bromoalkoxy)benzenes with paraformaldehyde, followed by Arbusov reaction with iso-propoxydiphenylphosphine. Solvent extrac...
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Veröffentlicht in: | RSC advances 2013-07, Vol.3 (30), p.12376-12383 |
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Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | A new class of pillar[5]arene-based phosphine oxides tethered with ten chelating groups on both rims of the pillar were synthesized viatwo steps from macrocyclization of 1,4-bis(bromoalkoxy)benzenes with paraformaldehyde, followed by Arbusov reaction with iso-propoxydiphenylphosphine. Solvent extraction of these ligands towards selected lanthanides and actinides was investigated under acidic condition. Compared with acyclic monovalent analogs and classical extractant tri-n-octylphosphine oxide (TOPO), the remarkable efficiency and selectivity for thorium(iv) and uranyl(vi) as observed in these novel extractants bearing a varying spacer length revealed the significance of preorganization of chelating groups on pillararene platform. Log-log plot analysis indicated the 1 : 1 stoichiometry (ligand/metal) for the extracted complex formed between the ligand and thorium(iv) or uranyl(vi). The extraction efficiency was considerably improved with increasing acidity in a range of 0.1-1.5 M HNO sub(3), a result that is distinct from the extraction behaviour of calixarene-based phosphine oxides. The extractability increased with enhancing NaNO sub(3) concentration and high salinity assisted the preferential extraction of U(vi) over Th(iv). These ligands also showed moderate efficiency in differentiating europium(iii) and americium(iii) at 1 M HNO sub(3) in the presence of a synergist (Br sub(6)-COSAN). |
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ISSN: | 2046-2069 |
DOI: | 10.1039/c3ra41251b |