ic6b01937_si_002.pdf (5.41 MB)
Polynuclear Bismuth Oxido Sulfonato Clusters, Polymers, and Ion Pairs from Bi2O3 under Mild Conditions
journal contribution
posted on 2016-10-14, 14:05 authored by Dimuthu C. Senevirathna, Victoria L. Blair, Melissa
V. Werrett, Philip C. AndrewsEight novel bismuth(III) sulfonato
compounds have been synthesized and characterized using the sonochemical
reaction of Bi2O3 with a range of sulfonic acids,
including 2,5-dimethylbenzenesulfonic acid (2,5-DMSH), 2,4-dinitrobenzenesulfonic acid (2,4-DNSH), 2,5-dichlorobenzenesulfonic
acid (2,5-DCSH), 1,2-benzenedisulfonic acid (1,2-BDSH2), 1,3-benzenedisulfonic acid (1,3-BDSH2), 2-sulfobenzoic acid (2-SBH2), 3-sulfobenzoic acid (3-SBH2), and 2-naphthalenesulfonic acid (NPSH). Six of
the complexes (1, 2, 4, and 6–8) were structurally characterized through
single-crystal X-ray crystallography. In the presence of the monosulfonic
acids 2,5-DMSH, 2,4-DNSH, and 2,5-DCSH, polynuclear bismuth(III) oxido clusters were isolated:
namely, [Bi6O4(OH)4(2,5-DMS)6(H2O)6]·10H2O (1·10H2O), [Bi6O4(OH)4(2,4-DNS)6(H2O)6]·6H2O (2·6H2O), and [Bi6O4(OH)4(2,5-DCS)6(H2O)6] (3). The disulfonic acid 1,3-BDSH2 also produced an oxido cluster: [Bi6O4(OH)4(1,3-BDS)3]·8H2O (5·8H2O). The remaining diacid ligands
(1,2-BDSH2, 2-SBH2, and 3-SBH2), upon reaction with
Bi2O3, produced polymeric Bi(III) sulfonato
complexes: namely [Bi(1,2-BDS)(OH)(H2O)2]∞ (4), [Bi(2-SB)(2-SBH)H2O]∞·2H2O (6·2H2O), and [NH2(Me)2]2[Bi2(3-SB)4]∞ (7). The larger NPSH ligand produced the monomeric
contact ion pair [Bi(NPS)2(H2O)6][NPS]·3H2O (8·3H2O), upon sonication with
Bi2O3.