A Simple Thermodynamic Model for Rationalizing the Formation of Self-Assembled Multimetallic Edifices: Application to Triple-Stranded Helicates - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of the American Chemical Society Année : 2004

A Simple Thermodynamic Model for Rationalizing the Formation of Self-Assembled Multimetallic Edifices: Application to Triple-Stranded Helicates

Kornelia Zeckert
  • Fonction : Auteur
Jean-Pierre Rivera
  • Fonction : Auteur
Sébastien Floquet
André Pinto
  • Fonction : Auteur
Michal Borkovec
  • Fonction : Auteur
  • PersonId : 861847
Claude Piguet

Résumé

Reaction of the bis-tridentate ligand bis[1-ethyl-2-[6'-(N,N-diethylcarbamoyl)pyridin-2'-yl]benzimidazol-5-yl]methane (L2) with Ln(CF(3)SO(3))(3).xH(2)O in acetonitrile (Ln = La-Lu) demonstrates the successive formation of three stable complexes [Ln(L2)(3)](3+), [Ln(2)(L2)(3)](6+), and [Ln(2)(L2)(2)](6+). Crystal-field independent NMR methods establish that the crystal structure of [Tb(2)(L2)(3)](6+) is a satisfying model for the helical structure observed in solution. This allows the qualitative and quantitative beta23 (bi,Ln1,Ln2)characterization of the heterobimetallic helicates [(Ln(1))(Ln(2))(L2)(3)](6+). A simple free energy thermodynamic model based on (i) an absolute affinity for each nine-coordinate lanthanide occupying a terminal N(6)O(3) site and (ii) a single intermetallic interaction between two adjacent metal ions in the complexes (DeltaE) successfully models the experimental macroscopic constants and allows the rational molecular programming of the extended trimetallic homologues [Ln(3)(L5)(3)](9+).

Domaines

Chimie

Dates et versions

hal-02122608 , version 1 (07-05-2019)

Identifiants

Citer

Kornelia Zeckert, Josef Hamacek, Jean-Pierre Rivera, Sébastien Floquet, André Pinto, et al.. A Simple Thermodynamic Model for Rationalizing the Formation of Self-Assembled Multimetallic Edifices: Application to Triple-Stranded Helicates. Journal of the American Chemical Society, 2004, 126 (37), pp.11589-11601. ⟨10.1021/ja0483443⟩. ⟨hal-02122608⟩
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