Linear Polynuclear Helicates as a Link between Discrete Supramolecular Complexes and Programmed Infinite Polymetallic Chains

The 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 processes


Published in:
Chemistry - A European Journal, 14, 10, 2994-3005
Year:
2008
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 Record created 2008-04-14, last modified 2018-03-17

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