ens, paris, 13-12-2007 "des caténanes et rotaxanes aux machines moléculaires"...
TRANSCRIPT
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
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
copper(I)-templated synthesis of a [2]catenane
Dietrich-Buchecker et al., Tet. Lett., 1983
gf
gf
"entwining"
"gathering and threading"
Dietrich-Buchecker et al., JACS, 1984
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)
Rastogi & Girvin, Nature, 1999
ATP synthase is the
most important
rotaxane of Nature.
It is also an amazing
rotary motor
a natural example :
-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
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
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)
N
N
N
NN
OO
O
OO
O
O
OCH3
CH3
CH3
=
(13 steps from 1,10-phenanthroline)
44
= Cu(I)
oriented cyclic array
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
[Cu(CH3CN)4]PF6
N
N
N
NN
OO
O
OO
O
O
OCH3
CH3
CH3
+ ?brown-red solution
acetonitrile
1
[1.Cu]nn+
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)
synthesis of the ring-filament conjugate (1)
synthesis of the ring-filament conjugate (2)
a [2]rotaxane tetramer consisting of two "filaments"
and two bis-macrocycles
Jean-Paul Collin, Julien Frey, Valérie Heitz and Christian Tock
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
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
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)
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
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 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
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
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
CNRS and Université Louis Pasteur (Strasbourg)
European Network (STREP) : MOLDYNLOGIC
European Network (STREP) : BIOMACH