1. "Des Caténanes et Rotaxanes aux Machines Moléculaires"
ENS, Paris,
"Des Caténanes et Rotaxanes aux Machines Moléculaires"
Jean-Pierre Sauvage

2. a [2]catenane
a [2]rotaxane
Until the mid 80s, these compounds seemed to be out of reach, although German chemists (Schill) could demonstrate that they can be obtained via elegant but low-yielding and multistep synthetic routes

3. The synthesis of topologicaly non trivial molecules is, in itself, a challenging task
the trefoil knot
Strasbourg,1989
the Borromean rings
UCLA, 2004
In the course of the last 20 years, many such systems have been made (challenge) and studied (new properties)

4. copper(I)-templated synthesis of a [2]catenane

5. "gathering and threading"gf
"entwining"
"gathering and threading"
Dietrich-Buchecker et al., Tet. Lett., 1983

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

7. OH
(27%)

8. (100%)

9. towards molecular machines and motors very active field of research!
Molecular machines and motors : "swimming in molasses and walking in a hurricane" (Dean Astumian)

10. a natural example :
ATP synthase is the most important rotaxane of Nature.
It is also an amazing rotary motor
Rastogi & Girvin, Nature, 1999

11. rotation of a ring within another ring (no directionality): use of the Cu(II)/Cu(I) couple (Livoreil et al., 1994)
-e-
+0.67 V
seconds
minutes
= Cu(I)
= Cu(II)
+e-
-0.06 V

13. the original two-position catenane (1994): several seconds to hours
In Strasbourg, since 1994, new systems have been designed and synthesised, with shorter and shorter response times
the original two-position catenane (1994): several seconds to hours
a pirouetting rotaxane, (5th generation, 2005): microseconds to milliseconds

14. towards a synthetic molecular "muscle"
Maria Consuelo Jiménez (Chelo)...Christiane Dietrich-Buchecker

15. A molecular "shuttle": the compound is set in motion by modifying the acceptor-donor interaction

16. Nature, Vol. 445, pp , January 25, 2007

17. Towards two-dimensional interlocking and threaded arrays

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

19. a natural chain-mail

20. a [2]rotaxane tetramer
Tomás Kraus (Strasbourg and Prague), Milos Budesinsky, Josef Cvacka (Prague)

21. (13 steps from 1,10-phenanthroline)=
(13 steps from 1,10-phenanthroline)

22. oriented cyclic array 4 4
= Cu(I)

24. CPK model of the tetramer
Tomás Kraus

25. [Cu(CH3CN)4]PF6 + ?
acetonitrile
brown-red solution
[1.Cu]nn+ 1

26. the tetramer is in equilibrium with the trimer
(concentrated solutions)
(dilute solutions)
the tetramer is in equilibrium with the trimer
acetonitrile 3 + , P F 6 -
very slow process (days)

27. synthesis of the ring-filament conjugate (1)

28. synthesis of the ring-filament conjugate (2)

29. Jean-Paul Collin, Julien Frey, Valérie Heitz and Christian Tock
a [2]rotaxane tetramer consisting of two "filaments" and two bis-macrocycles
Jean-Paul Collin, Julien Frey, Valérie Heitz and Christian Tock

30. the organic fragments
the two-chelate rod
the bis-macrocycle

31. copper(I)-induced threading of two bis-macrocycles on two rods: a cyclic [4]rotaxane
= spacer
= bidentate chelate
= Cu(I)
Jean-Paul Collin, Julien Frey, Valérie Heitz, Efstathia Sakellariou and Christian Tock

32. preliminary X-ray structure: Rissanen and coworkers, Jyväskylä

33. two-dimensional interlocking and threaded arrays
towards 2D polymers or non covalent assemblies
flexible but mechanically robust membranes
pores with an adjustable size
molecular "presses"

34. Mechanical switching of a surface-grafted [2]catenane by in-situ copper complexation
(J. Am. Chem. Soc., 2008)

35. 1Max-Planck-Institut für Festkörperforschung, Stuttgart
Dietmar Payer1, Stephan Rauschenbach1, Mitsuharu Konuma1, Chariya Virojanadara1, Ulrich Starke1, Christiane Dietrich-Buchecker2, Jean-Paul Collin2, Jean-Pierre Sauvage2, Nian Lin1*, Klaus Kern1,3
1Max-Planck-Institut für Festkörperforschung, Stuttgart
2Laboratoire de Chimie Organo-Minérale, Université Louis Pasteur/ U.M.R. du CNRS Strasbourg
3Institut de Physique des Nanostructures, Ecole Polytechnique Fédérale de Lausanne, Lausanne

36. Cu(I)
"cat-30"
"Cu cat-30"

37. The free catenane was deposited in UHV onto the Ag(111) surface by means of organic molecular beam epitaxy (OMBE), with the crucible containing the catenane powder constantly held at a temperature of 600 K
(a) STM topography of dimer chain structures of 1 at Ag(111) surface. The arrow points to a molecule sitting on top of a chain.

38. (b) High-resolution STM topography showing the uniform circular or oval shape molecules of 1; d1= 1.6 nm and d2= 2.1 nm
(c) A tentative model of the dimer chain structure derived from the STM data and the X-ray structure of 1; the overlapping phenanthroline units of the neighbouring molecules interact via - stacking

39. STM data showing the structural change of 1 adsorbed on Ag(111) upon copper addition : (a) chain structure, (b-d) gradual addition of Cu. Bright protrusion in (d) correspond to excess Cu (clusters)

40. the free [2]catenane can be deposited on a Ag(111) surface by sublimation at 600 K without chemical degradation
once the [2]catenane molecules are adsorbed on the Ag(111) surface, an in-situ Cu complexation induces a complete rearrangement of the system
Cu(I)
"cat-30"
"Cu cat-30" Ag

41. 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…Benoît Colasson…Pierre Mobian…Masatoshi Koizumi
Julie Voignier…Valérie Heitz
Catenanes and Knots
X-ray structures
Claudine Pascard…Michèle Césario (Gif-sur-Yvette)
Jean-Fischer…André De Cian…Nathalie Gruber
…Richard Welter (Strasbourg)

42. 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
pirouetting of a ring around the axle: Laurence Raehm...Jean-Marc Kern…Ingo Poleschak…Ulla Létinois…Jean-Paul Collin
towards molecular muscles : Maria Consuelo Jiménez (Chelo)...Christiane Dietrich-Buchecker
photochemically induced motions (Bologna): Nicola Armaroli...Vincenzo Balzani...Lucia Flamigni...Barbara Ventura

43. Two-dimensional threaded arrays
Tomás Kraus (Strasbourg and Prague), Milos Budesinsky, Josef Cvacka (Prague)
Jean-Paul Collin, Julien Frey, Valérie Heitz, Efstathia Sakellariou, Christian Tock, Valérie Sartor and Benoît Champin
Bi-isoquinoline ligands and their complexes
Fabien Durola & Oliver Wenger
Pirmin Roesel, David Hanss, Sasha Prykhodko
X-ray structures: André De Cian
Kari Rissanen et al. (Jyväskylä, Finland)

44. CNRS and Université Louis Pasteur (Strasbourg)
European Network (STREP) : MOLDYNLOGIC
European Network (STREP) : BIOMACH