Dynamic properties of a hexadecamolybdenum wheel: Studies in solution and density functional theory calculations

Ali Kachmar, Sébastien Floquet, Jean Françola Lemonnier, Emmanuel Cadot, Marie Madeleine Rohmer, Marc Bénard

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Variable temperature 1H NMR studies of the host-guest complex [Mo16O16S16(OH)16(H 2O)4(PDA)2]4- (1 ; PDA2- = phenylenediacetate) previously carried out in D2O have revealed a complex behavior in solution, Involving a gliding motion of both parallel phenyl rings of the PDA2- ligands. In the present work, we present new NMR spectra carried out in the aprotic solvent CD3CN, which allow the observation of the proton signals associated with the bridging hydroxo groups of the inorganic host. The new spectra provide detailed Information about the concerted reorganization of the guest components, that Is, PDA2- and water molecules. The existence of an equilibrium between two distinct isomers differing In the linking mode between the inorganic host and the two equivalent PDA2- ligands is evidenced. This equilibrium appears strongly dependent upon the temperature, leading to a complete inversion of the distribution between 300 and 226 K. The thermodynamic data related to the isomerization reaction have been determined (ΔrH= -50.5 kJ mol-1 and ΔrS= -215 J mol-1 K -1). Furthermore, at low temperature, one of the Isomers exists In two conformations, only differing in the H-bond network involving the inner water molecules. Density functional theory calculations were carried out to push ahead the interpretations obtained from experiment, identify the isomers of 1, and specify the role and the positions of the guest water molecules. Among the various structures that have been calculated for 1, three fall In a narrow energy range and should correspond to the species characterized by variable-temperature 1H NMR experiments in CD3CN. Finally, this study shows how the internal disposition of the ligands affects the ellipticity of the Mo16 ring which varies from one isomer to the other In the 0.73-1 range and highlights solvation of the ring as one of the key parameters for the conformational design of these flexible host-guest systems.

Original languageEnglish
Pages (from-to)6852-6859
Number of pages8
JournalInorganic Chemistry
Volume48
Issue number14
DOIs
Publication statusPublished - 20 Jul 2009
Externally publishedYes

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wheels
Isomers
dynamic characteristics
Density functional theory
Wheels
isomers
density functional theory
Temperature
Nuclear magnetic resonance
Ligands
nuclear magnetic resonance
ligands
Molecules
Water
rings
water
molecules
gliding
Personal digital assistants
Solvation

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Dynamic properties of a hexadecamolybdenum wheel : Studies in solution and density functional theory calculations. / Kachmar, Ali; Floquet, Sébastien; Lemonnier, Jean Françola; Cadot, Emmanuel; Rohmer, Marie Madeleine; Bénard, Marc.

In: Inorganic Chemistry, Vol. 48, No. 14, 20.07.2009, p. 6852-6859.

Research output: Contribution to journalArticle

Kachmar, Ali ; Floquet, Sébastien ; Lemonnier, Jean Françola ; Cadot, Emmanuel ; Rohmer, Marie Madeleine ; Bénard, Marc. / Dynamic properties of a hexadecamolybdenum wheel : Studies in solution and density functional theory calculations. In: Inorganic Chemistry. 2009 ; Vol. 48, No. 14. pp. 6852-6859.
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