Structure, Formation, and Dynamics of Mo12 and Mo16 Oxothiomolybdenum Rings Containing Terephtalate Derivatives - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Chemistry - A European Journal Année : 2007

Structure, Formation, and Dynamics of Mo12 and Mo16 Oxothiomolybdenum Rings Containing Terephtalate Derivatives

Résumé

The influence of rigid orsemirigid dicarboxylate anions,terephtalate (TerP2),isophtalate (IsoP2),and phenylenediacetate (PDA2) on the self-condensation process of the {Mo2O2S2]2+ dioxothio cation has been investigated. Three new molybdenum rings,[Mo 12O12S12(OH)) have been isolated and unambiguously characterized in the solid state by single-crystal X-ray studies and in solution by various NMR methods and especially by diffusion- correlated NMR (1H DOSY) spectroscopy,which was shown to be a powerful tool for the characterization and speciation of templated molybdenum ring systems in solution. Characterization by FT-IR and elemental analysis are also reported. The dynamic and thermodynamic properties of both the sixteen-membered rings were studied in aqueous medium. Specific and distinct behaviors were revealed for each system. The IsoP2/ACHTUNGTRENUNG[Mo2O2S2]2+ system gave rise to equilibrium,involving mono-templated [Mo12IsoP]2 and bis-templated [Mo(IsoP)2]4 ions. Thermodynamic parameters have been determined and showed that the driving- force for the formation of the [Mo16(IsoP)2]4 is entropically governed. However,whatever the conditions (temperature,proportio n of reactants), the PDA2/[Mo2O2S2]2+ system led only to a single compound,the [Mo16ACHTUNGTRENUNG(PDA)2]4 ion. The latter exhibits dynamic behavior,consisten t with the gliding of both the stacked aromatic groups. Stability and dynamics of both Mo16 rings was related to weak hydrophobic or pi–pi stacking inter-template interactions and inner hydrogen-bond network occurring within the [Mo16(IsoP)2]4 and [Mo16ACHTUNGTRENUNG(PDA)2]4 ions.

Dates et versions

hal-02310922 , version 1 (10-10-2019)

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Citer

Jean-François Lemonnier, Sébastien Floquet, Jérôme Marrot, Emmanuel Terazzi, Claude Piguet, et al.. Structure, Formation, and Dynamics of Mo12 and Mo16 Oxothiomolybdenum Rings Containing Terephtalate Derivatives. Chemistry - A European Journal, 2007, 13 (12), pp.3548-3557. ⟨10.1002/chem.200601369⟩. ⟨hal-02310922⟩
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