Dalla-Favera, NataliaHamacek, JosefBorkovec, MichalJeannerat, DamienGumy, FrédéricBünzli, Jean-Claude G.Ercolani, GianfrancoPiguet, Claude2008-04-142008-04-14200810.1002/chem.200701465https://infoscience.epfl.ch/handle/20.500.14299/20496WOS:000254872600006The contribution of the solvation energies to the assembly of polynuclear helicates reduces the free energy of intermetallic repulsion, DEMM, in condensed phase to such an extent that stable D3-symmetrical tetranuclear lanthanide-containing triplestranded helicates [Ln4(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 [Eu4(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 processeshelical structuresmulticomponent assemblypolynuclearstatistical factorsthermodynamicstext::journal::journal article::research article