ENS, Paris, 13-12 -2007 " Des Caténanes et Rotaxanes aux Machines Moléculaires "
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ENS, Paris, 13-12-2007
"Des Caténanes et Rotaxanes aux Machines Moléculaires"
Jean-Pierre Sauvage
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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
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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
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copper(I)-templated synthesis of a [2]catenane
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Dietrich-Buchecker et al., Tet. Lett., 1983
gf
gf
"entwining"
"gathering and threading"
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Dietrich-Buchecker et al., JACS, 1984
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OH (27%)
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(100%)
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towards molecular machines and motors
very active field of research!
Molecular machines and motors : "swimming in molasses and walking in a hurricane" (Dean Astumian)
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Rastogi & Girvin, Nature, 1999
ATP synthase is the
most important
rotaxane of Nature.
It is also an amazing
rotary motor
a natural example :
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-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)
+0.67 V
-0.06 V
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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
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a rotaxane dimer is the ideal topology for interconverting a streched structure and a contracted systemtowards a synthetic molecular "muscle"
Maria Consuelo Jiménez (Chelo)...Christiane Dietrich-Buchecker
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A molecular "shuttle": the compound is set in motion by modifying the acceptor-donor interaction
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Nature, Vol. 445, pp.414-417, January 25, 2007
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Towards two-dimensional interlocking and threaded arrays
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Topologically linked Protein Rings in the Bacteriophage HK97 Capsid
Wikoff, Liljas, Duda, Tsuruta, Hendrix and Johnson, Science, 2000
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a natural chain-mail
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a [2]rotaxane tetramer
Tomás Kraus (Strasbourg and Prague), Milos Budesinsky, Josef Cvacka (Prague)
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N
N
N
NN
OO
O
OO
O
O
OCH3
CH3
CH3
=
(13 steps from 1,10-phenanthroline)
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= Cu(I)
oriented cyclic array
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N
N N
O
OO O
O
O
OCH3
NNN
O
OO
OO
OOCH3
N
N
N N
OO O
O
O
OCH3
NNN
N
OO
OO
OOCH3
Cu
N
N
N N
O
OO O
O
O
OCH3
Cu
N
N NN
O
OO
OO
OH3CO
Cu
Cu
4+
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CPK model of the tetramer
Tomás Kraus
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[Cu(CH3CN)4]PF6
N
N
N
NN
OO
O
OO
O
O
OCH3
CH3
CH3
+ ?brown-red solution
acetonitrile
1
[1.Cu]nn+
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N
N N
O
OO O
O
O
OCH3
NNN
O
OO
OO
OOCH3
N
N
N N
OO O
O
O
OCH3
NNN
N
OO
OO
OOCH3
Cu
N
N
N N
O
OO O
O
O
OCH3
Cu
N
N NN
O
OO
OO
OH3CO
Cu
Cu
4+
(concentrated solutions) (dilute solutions)
the tetramer is in equilibrium with the trimer
acetonitrile
N
N
N
NN
OO
OO
O
O
OCH3
N
N
N
NN
OO
OO
O
O
OCH3
N NN N
N
O
OO
OO
OH3CO
Cu
Cu
Cu
3+, 3PF6-3+, 3PF6-
very slow process (days)
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synthesis of the ring-filament conjugate (1)
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synthesis of the ring-filament conjugate (2)
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a [2]rotaxane tetramer consisting of two "filaments"
and two bis-macrocycles
Jean-Paul Collin, Julien Frey, Valérie Heitz and Christian Tock
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N NN NOMeMeO
N
NN
N N
N
O
OO
O
O
O
O
O
O
O
O
O
the bis-macrocycle
the two-chelate rod
the organic fragments
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42
2
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
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preliminary X-ray structure: Rissanen and coworkers, Jyväskylä
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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"
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Mechanical switching of a surface-grafted [2]catenane by in-situ copper complexation
(J. Am. Chem. Soc., 2008)
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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,
Stuttgart2Laboratoire de Chimie Organo-Minérale, Université
Louis Pasteur/ U.M.R. du CNRS Strasbourg3Institut de Physique des Nanostructures, Ecole
Polytechnique Fédérale de Lausanne, Lausanne
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Cu(I)
"cat-30" "Cu cat-30"
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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.
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(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
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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)
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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
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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 KoizumiJulie 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
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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
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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
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CNRS and Université Louis Pasteur (Strasbourg)
European Network (STREP) : MOLDYNLOGIC
European Network (STREP) : BIOMACH