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Linear polynuclear helicates as a link between discrete supramolecular complexes and programmed infinite polymetallic chains.
Dalla-Favera, Natalia; Hamacek, Josef; Borkovec, Michal; Jeannerat, Damien; Gumy, Frédéric; Bünzli, Jean-Claude G; Ercolani, Gianfranco; Piguet, Claude.
Afiliação
  • Dalla-Favera N; Department of Inorganic, Analytical and Applied Chemistry, University of Geneva, 30 quai E. Ansermet, 1211 Geneva 4, Switzerland.
Chemistry ; 14(10): 2994-3005, 2008.
Artigo em Inglês | MEDLINE | ID: mdl-18293346
ABSTRACT
The contribution of the solvation energies to the assembly of polynuclear helicates reduces the free energy of intermetallic repulsion, DeltaE(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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Texto completo: Disponível Coleções: Bases de dados internacionais Base de dados: MEDLINE Idioma: Inglês Revista: Chemistry Assunto da revista: Química Ano de publicação: 2008 Tipo de documento: Artigo País de afiliação: Suíça