title: Host-guest adaptability within oxothiomolybdenum wheels: structures, studies in solution and DFT calculations.
abstract: The formation of host-guest cyclic architectures, built up through the self-condensation process of [Mo(2)O(2)S(2)](2+) oxothiocations around linear dicarboxylate ions such as adipate (Adip(2-)), suberate (Sub(2-)) and azelaate (Azel(2-)) anions is reported. The complexes [Mo(12)Adip](2-), [Mo(12)Sub](2-) and [Mo(14)Azel](2-) have been characterized in the solid state by X-ray diffraction and in solution by (1)H NMR in different solvents (D(2)O, DMF, DMSO and CD(3)CN). The host-guest dynamics appear to be dependent on the nature of the system and are mainly governed by mutual adaptability between the host and the guest. (1)H NMR DOSY experiments show systematic differences, either positive or negative between the experimental and calculated molecular weights which appear to be correlated with the charge of the anion. The relative stabilities of the twelve-membered rings containing the Adip(2-), Pim(2-) (pimelate) or Sub(2-) anions were determined experimentally and decrease according to the order [Mo(12)Adip](2-) > [Mo(12)Pim](2-) > [Mo(12)Sub](2-). The host-guest adaptability depends on the length of the carbon chain and gives rise to selective encapsulation processes. Finally, theoretical DFT investigations in the gas phase yielded conformations whose symmetry and geometrical parameters proved consistent with X-ray structures and (1)H NMR spectra recorded in DMSO or DMF. Energy calculation highlights the high flexibility of the ring showing that only 3.1 kJ mol(-1) accompanies the conformational change from circular to elliptical. The host-guest bond energy (Delta E) calculated for the Mo(12)-based clusters is consistent with the experimental stability scale, major variations being due to some constraints undergone by the central alkyl chain.
authors.affiliation: Institut Lavoisier de Versailles, UMR 8180, University of Versailles, 45 avenue des Etats Unis, 78035, Versailles, France.
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Lemonnier
authors.forename: Sébastien
authors.initials: S
authors.lastname: Floquet
authors.forename: Ali
authors.initials: A
authors.lastname: Kachmar
authors.forename: Marie-Madeleine
authors.initials: MM
authors.lastname: Rohmer
authors.forename: Marc
authors.initials: M
authors.lastname: Bénard
authors.forename: Jerôme
authors.initials: J
authors.lastname: Marrot
authors.forename: Emmanuel
authors.initials: E
authors.lastname: Terazzi
authors.forename: Claude
authors.initials: C
authors.lastname: Piguet
authors.forename: Emmanuel
authors.initials: E
authors.lastname: Cadot
mesh_terms: D002264:Carboxylic Acids / Q000737:chemistry; D003198:Computer Simulation; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D012996:Solutions; D012997:Solvents; D013696:Temperature
chemical_list: D002264:Carboxylic Acids; D012996:Solutions; D012997:Solvents; D008982:Molybdenum