Jean-Claude Bunzli - Mono- and polymetallic lanthanide-containing functional assemblies: a field between tradition and novelty

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  Piguet,C., Bunzli,J.C.G. Chemical Society Reviews  1999 28 (6) 347-358

  Abstract: The variable and versatile   co-ordination behaviour of lanthanide metal ions, Ln(III), limits   their selective introduction into organised molecular or   supramolecular architectures. The design of lanthanide-based   devices is thus a special challenge since their specific   electronic, magnetic or spectroscopic properties result from a   precise control of the co-ordination sphere around the metal   ions. The lock-and-key principle associated with the   preorganisation of rigid macropolycylic multidentate ligands   tailored for one particular Ln(III) only partially fulfils these   structural requirements. The development of less constrained   macrocyclic ligands or macrocycles bearing pendant arms allows a   smooth transition toward flexible (predisposed) receptors leading   to the application of the induced fit principle in lanthanide   co-ordination chemistry. According to this concept, programmed   secondary non-covalent interstrand interactions (pi-stacking,   hydrogen bonds, electrostatic repulsion) assist the complexation   process leading to an ultrafine tuning of the metallic   co-ordination sites. These two complementary approaches are   discussed and evaluated for the design of organised mono-, di-   and polymetallic lanthanide complexes together with the   consideration of new semirigid multidentate podands which combine   both aspects

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