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

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

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)

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

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

Dietrich-Buchecker et al., JACS, 1984

OH (27%)

(100%)

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

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

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

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

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

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

Nature, Vol. 445, pp.414-417, January 25, 2007

Towards two-dimensional interlocking and threaded arrays

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

a natural chain-mail

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

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

oriented cyclic array 4 4 = Cu(I)

CPK model of the tetramer Tomás Kraus

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

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)

synthesis of the ring-filament conjugate (1)

synthesis of the ring-filament conjugate (2)

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

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

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

preliminary X-ray structure: Rissanen and coworkers, Jyväskylä

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"

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

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

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

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.

(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

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)

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

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)

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

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)

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