Jean-Claude Bunzli - Linear polynuclear helicates as a link between discrete supramolecular complexes and programmed infinite polymetallic chains

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  Dalla-Favera,N., Hamacek,J., Borkovec,M., Jeannerat,D., Gumy,F.,   Bunzli,J.C.G., Ercolani,G., Piguet,C. Chemistry-A European   Journal 2008 14 (10) 2994-3005

  Abstract: The contribution of the solvation   energies to the assembly of polynuclear helicates reduces the   free energy of intermetallic repulsion, Delta E(MM), in condensed   phase to such an extent that stable D(3)-symmetrical tetranuclear   lanthanide-containing triple-stranded helicates   [Ln(4)(L4)(3)](12+) are quantitatively produced at millimolar   concentrations, despite the twelve positive charge borne by these   complexes. A detailed modelling of the formation constants using   statistical factors, adapted to self-assembly processes involving   intra- and intermolecular connections, provides a set of five   microscopic parameters, which can be successfully used for   rationalizing the stepwise generation of linear bi-, tri- and   tetranuclear analogues. Photophysical studies of   [Eu(4)(L4)(3)](12+) confirm the existence of two different   binding sites producing differentiated metal-centred emission at   low temperature, which transforms into single site luminescence   at room temperature because of intramolecular energy funelling   processes

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