Polynuclear Bismuth Oxido Sulfonato Clusters, Polymers, and Ion Pairs from BiO under Mild Conditions.

Eight novel bismuth(III) sulfonato compounds have been synthesized and characterized using the sonochemical reaction of BiO 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-BDSH), 1,3-benzenedisulfonic acid (1,3-BDSH), 2-sulfobenzoic acid (2-SBH), 3-sulfobenzoic acid (3-SBH), 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, [BiO(OH)(2,5-DMS)(HO)]·10HO (1·10HO), [BiO(OH)(2,4-DNS)(HO)]·6HO (2·6HO), and [BiO(OH)(2,5-DCS)(HO)] (3). The disulfonic acid 1,3-BDSH also produced an oxido cluster: [BiO(OH)(1,3-BDS)]·8HO (5·8HO). The remaining diacid ligands (1,2-BDSH, 2-SBH, and 3-SBH), upon reaction with BiO, produced polymeric Bi(III) sulfonato complexes: namely [Bi(1,2-BDS)(OH)(HO)] (4), [Bi(2-SB)(2-SBH)HO]·2HO (6·2HO), and [NH(Me)][Bi(3-SB)] (7). The larger NPSH ligand produced the monomeric contact ion pair [Bi(NPS)(HO)][NPS]·3HO (8·3HO), upon sonication with BiO.