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catenane

rotaxane. catenane. knot. Schill and coworkers. 1 =. 2 =. Topologically linked Protein Rings in the Bacteriophage HK97 Capsid Wikoff, Liljas, Duda, Tsuruta, Hendrix and Johnson, Science , 2000. a natural "coat of mail". gf. gf. Dietrich-Buchecker et al., Tet. Lett., 1983.

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catenane

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  1. rotaxane catenane knot

  2. Schill and coworkers 1 = 2 =

  3. Topologically linked Protein Rings in the Bacteriophage HK97 Capsid Wikoff, Liljas, Duda, Tsuruta, Hendrix and Johnson, Science, 2000

  4. a natural "coat of mail"

  5. gf gf Dietrich-Buchecker et al., Tet. Lett., 1983

  6. Dietrich-Buchecker et al., JACS, 1984

  7. OH

  8. synthesis of catenanes following a one-step strategy entwining of two open-chain fragments around Cu(I) followed by Ring-Closing Metathesis (RCM) of terminal olefins 92% yield (isolated) Grubbs & Weck / Mohr

  9. using 27-membered rings as peripheral units, multiring interlocking systems could be obtained 132-memberd central ring

  10. Stoddart et al. Hunter Vögtle and coworkers

  11. Towards Rotary Motors A copper-containing catenane whose rings rotate between two positions without direction control

  12. ATP synthase is the most important rotaxane of Nature Rastogi & Girvin, Nature, 1999

  13. = Cu(I) = Cu(II) rotation of a ring within another ring (no directionality): use of the Cu(II)/Cu(I) couple Livoreil et al., 1994

  14. = Cu(II) = Cu(I) -e- seconds Livoreil et al., 1994 minutes +e-

  15. a [2]catenane with three distinct situations : rotation of both rings within the other ring each ring incorporates both a bi- and a tri-dentate coordinating unit

  16. molecular shuttles: gliding of a ring along the axle on which it is threaded signal 1 signal 2

  17. Science, Vol. 294, 21 December 2001, p.2442

  18. (A) Molecular drawing of the bistable [2]catenane used in this work. The voltage-driven circumrotation of co-conformer [A0] to co-conformer [B+] is the basis of the device.

  19. (B) Proposed mechanism for the operation of the device. Co-conformer [A0] represents both the ground-state structure of the [2]catenane and the “switch open” state of the device. When the [2]catenane is oxidized, the TTF groups (green) are ionized. The coconformer [B+] is formed. When the voltage is reduced to a near-zero bias, the co-conformer [B0] is formed, and this represents the “switch closed” state of the device. Partial reduction of the cyclophane (+2 V) is necessary to regenerate the [A0] co-conformer. The reduced co-conformer [AB#] is indicated with an unknown oxidation state.

  20. towards a synthetic molecular "muscle" a copper-complexed rotaxane dimer whose overall length can be modified by a chemical signal

  21. Maria Consuelo Jiménez (Chelo) and Christiane Dietrich-Buchecker

  22. the key step : formation of the rotaxane dimer ?

  23. formation of the rotaxane dimer

  24. X-ray structure of the doubly threaded species

  25. the two states of the "muscle" extended ~ 85 Å = Zn2+ contracted ~ 65 Å

  26. Synthesis and Coordination Chemistry Laboratoire de Chimie Organo-Minérale (Strasbourg) Christiane Dietrich-Buchecker...Jean-Claude Chambron... Jean-Marc Kern...Jean Weiss... Abdel Klemiss... Dennis Mitchell... Catherine Hemmert... Jean Weiss...Jean-François Nierengarten... Jean-Luc Weidmann...Gwénaël Rapenne... David Amabilino...Aude Livoreil...Riccardo Carina... Bernhard Mohr...Neri Geum Hwang…Christine Hamann Catenanes and Knots X-ray structures Claudine Pascard et al. (Gif-sur-Yvette) Jean-Fischer…André De Cian…Nathalie Gruber …Richard Welter (Strasbourg)

  27. Copper-complexed Catenanes and Rotaxanes in Motion • catenanes in motion : Aude Livoreil...Diego J. Cardenas • translation of a ring along an axle : Jean-Paul Collin... Pablo Gaviña • oscillation/rotation of an axle inside a wheel : Laurence Raehm...Jean-Marc Kern • towards molecular muscles : Maria Consuelo Jiménez (Chelo)...Christiane Dietrich-Buchecker • photochemically induced motions (Bologna) : Nicola Armaroli...Vincenzo Balzani...Lucia Flamigni...Barbara Ventura

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