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首页> 外文期刊>Crystal growth & design >Supramolecular Two-Dimensional Network Mediated via Sulfur's sigma-Holes in a Conducting Molecular Crystal: Effects of Its Rigidity on Physical Properties and Structural Transition
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Supramolecular Two-Dimensional Network Mediated via Sulfur's sigma-Holes in a Conducting Molecular Crystal: Effects of Its Rigidity on Physical Properties and Structural Transition

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This study reveals that noncovalent intermolecular interactions mediated by sigma-holes on sulfur atoms can function as an efficient tool to design and construct a novel supramolecular motif, and that these noncovalent bonds are rigid enough to regulate the displacement of molecules at the structural transition. A novel two-dimensional cation anion supramolecular structure via sulfur's sigma-holes was constructed in a functional molecular crystal, (ethyl-4-bromothiazolium)(2)Pt-(mnt)(2)(3) (mnt = maleonitriledithiolato). The unit cell contained two crystallographically independent anions A and B. Electrostatic sigma-hole bonds were detected between sigma-holes on sulfur in the cation and lone pairs of -CN moieties in B, while A did not form such S center dot center dot center dot N sigma-hole bonds. This salt exhibited a structural transition at ca. 150 K, in which B did not show apparent displacement, while A shifted along the anion's stacking direction. This shift enhanced trimerization of the anion in the low-temperature phase, leading to the enhanced antiferromagnetic exchange interaction and the increased activation energy in the electrical conduction. We showed that "sulfur-based sigma-hole bonds are rigid enough to contribute to modulating the physical properties through regulating the displacement of molecules in molecular materials.

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