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Thermodynamics, Structure and Properties of Polynuclear Lanthanide Complexes with a Tripodal Ligand: Insight into their Self-Assembly

  1. Dr. Josef Hamacek1,*,
  2. Dr. Céline Besnard2,
  3. Dr. Tiphaine Penhouet3,
  4. Dr. Pierre-Yves Morgantini3

Article first published online: 5 MAY 2011

DOI: 10.1002/chem.201100173

Issue

Chemistry - A European Journal

Chemistry - A European Journal

Volume 17, Issue 24, pages 6753–6764, June 6, 2011

Additional Information

How to Cite

Hamacek, J., Besnard, C., Penhouet, T. and Morgantini, P.-Y. (2011), Thermodynamics, Structure and Properties of Polynuclear Lanthanide Complexes with a Tripodal Ligand: Insight into their Self-Assembly. Chem. Eur. J., 17: 6753–6764. doi: 10.1002/chem.201100173

Author Information

  1. 1

    Department of Inorganic, Analytical and Applied Chemistry, University of Geneva, 30 quai E.-Ansermet, 1211 Geneva 4 (Switzerland), Fax: (+41) 22-379-6830

  2. 2

    Laboratory of X-ray Crystallography, University of Geneva, 24 quai E.-Ansermet, 1211 Geneva 4 (Switzerland)

  3. 3

    Department of Physical Chemistry, University of Geneva, 30 quai E.-Ansermet, 1211 Geneva 4 (Switzerland)

*Department of Inorganic, Analytical and Applied Chemistry, University of Geneva, 30 quai E.-Ansermet, 1211 Geneva 4 (Switzerland), Fax: (+41) 22-379-6830

Publication History

  1. Issue published online: 26 MAY 2011
  2. Article first published online: 5 MAY 2011
  3. Manuscript Received: 17 JAN 2011

Funded by

  • University of Geneva
  • SNF

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Keywords:

  • helical structures;
  • lanthanides;
  • polynuclear complexes;
  • thermodynamics;
  • tripodal ligands

Abstract

Self-assembly processes between a tripodal ligand and LnIII cations have been investigated by means of supramolecular analytical methods. At an equimolar ratio of components, tetranuclear tetrahedral complexes are readily formed in acetonitrile. The structural analysis of the crystallographic data shows a helical wrapping of binding strands around metallic cations. The properties of this series of highly charged 3D compounds were examined by using NMR spectroscopy and optical methods in solution and in the solid state. In the presence of excess metal, a new trinuclear complex was identified. The X-ray crystal structure elucidated the coordination of metallic cations with two ligands of different conformations. By varying the metal/ligand ratio, a global speciation of this supramolecular system has been evidenced with different spectroscopic methods. In addition, these rather complicated equilibria were successfully characterised with the thermodynamic stability constants. A rational analysis of the self-assembly processes was attempted by using the thermodynamic free energy model and the impact of the ligand structure on the effective concentration is discussed.

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