Three new polyoxometalate (POM) supramolecular assemblies constructed from phosphotungstate clusters and S-containing pyridine-based cations had been successfully isolated and characterized. Structural analysis revealed that their formula were (H₂PySSPy)₃[PW₁₂O₄₀]₂·6H₂O (1), (H_3/2PySPy)₂[PW₁₂O₄₀]·6H₂O (2) and [Ag(HPyS)]₄[Ag₈(H₂O)₉][P₂W₁₈O₆₂]₂·4H₂O (3) (PySSPy = 4,4′-dipyridine disulfide; PySPy = 4,4′-thiodipyridine; PySH = pyridine-4-thiol), respectively. The three crystals were assembled by means of multiple weak intermolecular cooperative interactions of hydrogen bonding, S⋯O, C–H⋯π, etc. In particular, the peculiar supramolecular bond of the ‘polyanion–π’ binding interaction between the polyanion receptor and the six-membered pyridine ring was described in some detail. These complex and noncovalent contacts efficiently induce the construction of the crystal supramolecular lattices of 1–3. During the formation process of 2 and 3, organic moieties were achieved through the in situ cleavage of S–S chemical bonds in PySSPy. Crystal 3 contains a 3D network constructed from Dawson-like polyanions and Ag–PyS cationic units through Ag–O and Ag–S coordination bonds. One anionic [P₂W₁₈O₆₂]⁶⁻ cluster is bonded to eighteen Ag ions through many Ag–O interactions, presenting an interesting Ag₁₈-supported Dawson structure.

中文翻译：

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超分子协同相互作用诱导的磷钨酸多阴离子和含硫吡啶基阳离子的组装†

从磷钨酸盐簇和含S的吡啶基阳离子构建的三个新的多金属氧酸盐（POM）超分子组装已成功分离和表征。结构分析表明，它们的分子式为（H ₂ PySSPy）₃ [PW ₁₂ O ₄₀ ] ₂ ·6H ₂ O（1），（H _3/2 PySPy）₂ [PW ₁₂ O ₄₀ ]·6H ₂ O（2）和[Ag（HPyS）] ₄ [Ag ₈（H ₂ O）₉ ] [P ₂ W ₁₈ O₆₂ ] ₂ ·4H ₂ O（ 3）（PySSPy = 4,4'-联吡啶二硫化物； PySPy = 4,4'-硫代二吡啶； PySH =吡啶-4-硫醇）。这三个晶体是通过氢键，S⋯O，C–H⋯π等的多个弱分子间协作相互作用而组装的。特别是，聚阴离子受体与聚阴离子之间的'聚阴离子-π'结合相互作用的特殊超分子键详细描述了六元吡啶环。这些复杂且非共价的接触有效地诱导了1-3的超分子晶格的构建。在2和3的形成过程中，通过形成有机部分。PySSPy中S–S化学键的原位切割。晶体3包含一个3D网络，该网络由Dawson型聚阴离子和Ag-PyS阳离子单元通过Ag-O和Ag-S配位键构成。一个阴离子[P ₂ W ₁₈ O ₆₂ ] ⁶⁻团簇通过许多Ag-O相互作用键合到18个Ag离子上，呈现出有趣的Ag ₁₈支撑的道森结构。