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Transition-Metal-Complexed Cyclic [3]- and [4]Pseudorotaxanes Containing Rigid Ring-and-Filament Conjugates: Synthesis and Solution Studies

Authors

  • Dr. Julie Voignier,

    1. Laboratoire de Chimie Organo-Minérale, Institut de Chimie, Université de Strasbourg-CNRS/UMR 7177, 4, rue Blaise Pascal, 67070 Strasbourg-Cedex (France), Fax: (+33) 390-241-368
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  • Dr. Julien Frey,

    1. Laboratoire de Chimie Organo-Minérale, Institut de Chimie, Université de Strasbourg-CNRS/UMR 7177, 4, rue Blaise Pascal, 67070 Strasbourg-Cedex (France), Fax: (+33) 390-241-368
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  • Dr. Tomáš Kraus,

    Corresponding author
    1. Institute of Organic Chemistry and Biochemistry AS CR, v.v.i. Flemingovo nám. 2, 166 10 Prague 6 (Czech Republic)
    • Institute of Organic Chemistry and Biochemistry AS CR, v.v.i. Flemingovo nám. 2, 166 10 Prague 6 (Czech Republic)
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  • Dr. Miloš Buděšínský,

    1. Institute of Organic Chemistry and Biochemistry AS CR, v.v.i. Flemingovo nám. 2, 166 10 Prague 6 (Czech Republic)
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  • Dr. Josef Cvačka,

    1. Institute of Organic Chemistry and Biochemistry AS CR, v.v.i. Flemingovo nám. 2, 166 10 Prague 6 (Czech Republic)
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  • Prof. Valérie Heitz,

    Corresponding author
    1. Laboratoire de Chimie Organo-Minérale, Institut de Chimie, Université de Strasbourg-CNRS/UMR 7177, 4, rue Blaise Pascal, 67070 Strasbourg-Cedex (France), Fax: (+33) 390-241-368
    • Laboratoire de Chimie Organo-Minérale, Institut de Chimie, Université de Strasbourg-CNRS/UMR 7177, 4, rue Blaise Pascal, 67070 Strasbourg-Cedex (France), Fax: (+33) 390-241-368
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  • Dr. Jean-Pierre Sauvage

    Corresponding author
    1. Laboratoire de Chimie Organo-Minérale, Institut de Chimie, Université de Strasbourg-CNRS/UMR 7177, 4, rue Blaise Pascal, 67070 Strasbourg-Cedex (France), Fax: (+33) 390-241-368
    • Laboratoire de Chimie Organo-Minérale, Institut de Chimie, Université de Strasbourg-CNRS/UMR 7177, 4, rue Blaise Pascal, 67070 Strasbourg-Cedex (France), Fax: (+33) 390-241-368
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Abstract

By using the “gathering-and-threading” effect of copper(I) with rigid ring-and-string conjugates, daisy-chain-type [3]- and [4]pseudorotaxanes could be prepared in high yields. The organic fragment used consisted of a 2,9-diphenyl-1,10-phenanthroline (dpp)-containing ring attached to a coordinating filament capable of threading through the ring of another molecule by coordination to copper(I). The bidentate chelate introduced in the axis was also a 1,10-phenanthroline (phen) derivative with two methyl groups ortho to the nitrogen atoms of the phen unit. The organic component was prepared following a multistep strategy, one of the key steps being the attachment of the ring to the lateral axis. This connection was done by a condensation reaction between an ortho dione located at the back of a ring-incorporated phen and an aromatic aldehyde, which was the end-function of the thread. An oxazole nucleus was obtained after the condensation, which provided a rigid connection between the ring and the axis. In this way, the coordination axes of the ring-incorporated bidentate chelate and of the ligand belonging to the lateral filament were approximately orthogonal to one another. The design was such that the tetrameric complex, a [4]pseudorotaxane, seemed to be the most stable species, owing to the mutual geometrical arrangement of the filament and the ring. Various spectroscopic techniques, such as 1H NMR spectroscopy, including DOSY, and electrospray ionization mass spectroscopy (ESI-MS), clearly demonstrated that a mixture of cyclic [3]- and [4]pseudorotaxane was obtained; the proportions of both components depended on concentration and temperature. Copper(I) was not the only metal center leading to the formation of cyclic pseudorotaxanes. A similar effect was observed with silver(I) as the templating metal: quantitative formation of threaded species was observed, with a higher proportion of trimer over tetramer than in the copper(I) case. Concentration and temperature effects were investigated for both series of CuI- and AgI-complexed threaded species showing that formation of the trimer was favored upon dilution or heating of the solution.

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