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. 2003 Oct 14;100(21):11970-4.
doi: 10.1073/pnas.1534925100. Epub 2003 Sep 29.

Self-organization by selection: generation of a metallosupramolecular grid architecture by selection of components in a dynamic library of ligands

Jonathan R Nitschke  1 , Jean-Marie Lehn
Affiliations

Self-organization by selection: generation of a metallosupramolecular grid architecture by selection of components in a dynamic library of ligands

Jonathan R Nitschke et al. Proc Natl Acad Sci U S A. .

Abstract

Self-organization by selection is implemented in the generation of a tetranuclear [2 x 2] grid-type metallosupramolecular architecture from its components. It occurs through a two-level self-assembly involving two dynamic processes: reversible covalent bound connection and reversible metal ion coordination. Thus, mixing the aminophenol 3, the dialdehyde 4, and zinc acetate generates the grid complex 1a(Zn) via the assembly of the ligand 2a by imine formation and of the grid by zinc(II) binding. When the same process is conducted in a solution containing a mixture of different aminophenol and carbonyl components, the generation of the grid 1a(Zn) drives the selection of the correct components in a virtual dynamic library of ligands, displaying an amplification factor of >100 and a selectivity of >99%. Component exchange as well as reversible protonic modulation of the assembly/disassembly process display the dynamic character of the system and its ability to respond/adapt to changes in environmental conditions. The processes described demonstrate the implementation of a two-level self-organization by selection operating on the dynamic diversity generated by a set of reversibly connected components and driven by the formation of a specific product in a "self-design" fashion.

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Figures

Fig. 1.
Fig. 1.
Two-component, two-level self-assembly of the [2 × 2] grid complexes 1a(M) in the case M = Zn.
Scheme 1.
Scheme 1.
Structures of the ligands 2 a–c.
Fig. 2.
Fig. 2.
Schematic representation of a poorly resolved x-ray structure of the [2 × 2] grid complex 1a(Zn).
Fig. 3.
Fig. 3.
Self-organization of the [2 × 2] grid 1a(Zn) by dynamic selection from a VCL of ligands.
Fig. 4.
Fig. 4.
Dynamic processes of [2 × 2] grid complexes: protonic modulation of the breakdown and reconstruction of 1a(Zn) (Left) and dynamic exchange of its ligand components (Right) to give 1c(Zn).
Fig. 5.
Fig. 5.
Distribution of the [2 × 2] grid species 1a(Zn) (○) and its components (•) as a function of the acidity of the medium (pD).
See this image and copyright information in PMC

References

    1. Lehn, J.-M. (1995) Supramolecular Chemistry: Concepts and Perspectives (VCH, Weinheim, Germany), pp. 139–197.
    1. Philp, D. & Stoddart, J. F. (1996) Angew. Chem. Int. Ed. Engl. 35, 1154–1196.
    1. Lehn, J.-M. (1999) in Supramolecular Science: Where It Is and Where It Is Going, eds. Ungaro, R. & Dalcanale, E. (Kluwer, Dordrecht, The Netherlands), pp. 287–304.
    1. Atwood, J. L., Davies, J. E. D., MacNicol, D. D., Vögtle, F. & Lehn, J.-M., eds. (1996) Comprehensive Supramolecular Chemistry (Pergamon, Oxford), Vol. 9.
    1. Swiegers, G. F. & Malefetse, T. J. (2000) Chem. Rev. (Washington, D.C.) 100, 3483–3537. - PubMed

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