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ENS, Paris, 13-12-2007 "Des Caténanes et Rotaxanes aux Machines Moléculaires" Jean-Pierre Sauvage.

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Presentation on theme: "ENS, Paris, 13-12-2007 "Des Caténanes et Rotaxanes aux Machines Moléculaires" Jean-Pierre Sauvage."— Presentation transcript:

1 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 In the course of the last 20 years, many such systems have been made (challenge) and studied (new properties) the Borromean rings Strasbourg,1989 UCLA, 2004 the trefoil knot

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

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

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

11 -e - +e - seconds minutes = 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) V V


13 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)

22 4 4 = Cu(I) oriented cyclic array


24 CPK model of the tetramer Tomás Kraus

25 [Cu(CH 3 CN) 4 ]PF 6 + ? brown-red solution acetonitrile 1 [1.Cu] n n+

26 (concentrated solutions)(dilute solutions) the tetramer is in equilibrium with the trimer acetonitrile 3+, 3PF6- very slow process (days)

27 synthesis of the ring-filament conjugate (1)

28 synthesis of the ring-filament conjugate (2)

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

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

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

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 Dietmar Payer 1, Stephan Rauschenbach 1, Mitsuharu Konuma 1, Chariya Virojanadara 1, Ulrich Starke 1, Christiane Dietrich-Buchecker 2, Jean-Paul Collin 2, Jean-Pierre Sauvage 2, Nian Lin 1*, Klaus Kern 1,3 1 Max-Planck-Institut für Festkörperforschung, Stuttgart 2 Laboratoire de Chimie Organo-Minérale, Université Louis Pasteur/ U.M.R. du CNRS Strasbourg 3 Institut 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; d 1 = 1.6 nm and d 2 = 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 Claudine Pascard…Michèle Césario (Gif-sur-Yvette) Jean-Fischer…André De Cian…Nathalie Gruber …Richard Welter (Strasbourg) X-ray structures

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 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) 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

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

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