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Supramolecular cooperative interactions induced assembly of phosphotungstatic polyanions and sulfur-containing pyridine-based cations

Abstract

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), (H3/2PySPy)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. Three crystals were assembled by means of multiple weak intermolecular cooperative interactions of hydrogen bonding, S∙∙∙O, and C-H∙∙∙π, etc. Especially, the peculiar supramolecular bond of ‘polyanion-π’ binding interaction between polyanion receptor and six-membered pyridine ring was described in some detail. These complex and noncovalent contacts efficiently induce the construction of 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 by eighteen Ag ions through more Ag-O interactions, presenting an interesting Ag18-supported Dawson structure.

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Publication details

The article was received on 06 Jan 2018, accepted on 07 Feb 2018 and first published on 07 Feb 2018


Article type: Paper
DOI: 10.1039/C8CE00026C
Citation: CrystEngComm, 2018, Accepted Manuscript
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    Supramolecular cooperative interactions induced assembly of phosphotungstatic polyanions and sulfur-containing pyridine-based cations

    X. Tian, X. Xin, Y. Gao and Z. Han, CrystEngComm, 2018, Accepted Manuscript , DOI: 10.1039/C8CE00026C

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