The synthesis and characterization of six homo‐ and heteroleptic coordination polymers and oxido clusters of bismuth(III) vinylsulfonates are reported. The solvent‐mediated reaction of BiPh₃ and vinylsulfonic acid in ethanol produces [{Ph₂Bi(O₃SCH=CH₂)}_n] (1), which crystallizes as a one‐dimensional coordination polymer as a result of bridging sulfonato ligands accompanied by intermolecular Bi⋅⋅⋅ π(arene) London dispersion interactions. In solution, compound 1 equilibrates to give [{PhBi(O₃SCH=CH₂)₂}_n] (2) and BiPh₃. Compound 2 is obtained as a single product by the reaction of BiPh₃ with vinylsulfonic acid in acetonitrile and crystallizes as a one‐dimensional coordination polymer. The homoleptic vinylsulfonate [{Bi(O₃SCH=CH₂)₃}_n] (3) was isolated as a two‐dimensional coordination polymer, which is quite moisture sensitive, but did not provide a distinct polynuclear bismuth oxido cluster upon hydrolysis. However, by treatment of [Bi₆O₄(OH)₄(NO₃)₆]⋅H₂O or [Bi₃₈O₄₅(OMc)₂₄(dmso)₉(H₂O)₂]⋅2 DMSO⋅5 H₂O (OMc=methacrylate) with vinylsulfonic acid, such a cluster, namely, [Bi₉O₇(OH)(O₃SCH=CH₂)₁₁(dmso)₁₁](O₃SCH=CH₂)⋅3 DMSO (4), is available as the main product. Starting from the hexanuclear bismuth oxido nitrate, another cluster, [Bi₃₈O₄₅(NO₃)₈(O₃SCH=CH₂)₁₄(dmso)₁₈](O₃SCH=CH₂)₂⋅2 DMSO (5), was observed as a co‐crystallizing side product, which upon further hydrolysis afforded [Bi₃₈O₄₅(NO₃)₆(OH)₄(O₃SCH=CH₂)₁₂(dmso)₂₃(H₂O)₂](O₃SCH=CH₂)₂⋅2 H₂O (6).

中文翻译：

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乙烯基磺酸铋（III）的同相和异相配位聚合物和氧化簇

报道了六种均相和杂配的配位聚合物和乙烯基磺酸铋（III）的氧化簇的合成和表征。溶剂介导的BiPh ₃与乙烯基磺酸在乙醇中的反应产生[{Ph ₂ Bi（O ₃ SCH = CH ₂）} _n ]（1），由于桥接磺基配体，其结晶为一维配位聚合物伴随着分子间Bi⋅⋅⋅π（arene）London色散相互作用。在溶液中，化合物1平衡生成[{PhBi（O ₃ SCH = CH ₂）₂ } _n ]（2）和BiPh ₃。化合物2是通过BiPh ₃与乙烯基磺酸在乙腈中反应得到的单一产物，并结晶为一维配位聚合物。均一的乙烯基磺酸盐[{Bi（O ₃ SCH = CH ₂）₃ } _n ]（3）被分离为二维配位聚合物，对水分非常敏感，但在水解时未提供明显的多核铋氧化簇。然而，通过处理[Bi ₆ O ₄（OH）₄（NO ₃）₆ ]·H ₂ O或[Bi ₃₈ O ₄₅（OMc）₂₄（dmso）₉（H ₂ O）₂ ]⋅2DMSO⋅5H ₂ O（OMc =甲基丙烯酸酯）与乙烯基磺酸，这样的簇，即[Bi ₉ O ₇（OH）（O ₃ SCH）主要产品为= CH ₂）₁₁（dmso）₁₁ ]（O ₃ SCH = CH ₂）⋅3DMSO（4）。从六核氧化铋硝酸铋开始，另一个簇[Bi ₃₈ O ₄₅（NO ₃）₈（O ₃ SCH = CH ₂）₁₄（dmso）₁₈ ]（O ₃ SCH = CH ₂）₂ ⋅2DMSO（5）中，观察到作为共结晶副产物，其在进一步水解，得到[毕₃₈ ø ₄₅（NO ₃）₆（OH）₄（O ₃ SCH = CH ₂）₁₂（DMSO）₂₃（H ₂ O）₂ ]（O ₃ SCH = CH ₂）₂ ⋅2ħ ₂ O（6）。