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copper-complexed i̇nterlocki̇ng compounds and molecular

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copper-complexed i̇nterlocki̇ng compounds and molecular
3rd International Summer School
“Supramolecular Systems in
Chemistry and
Biology”
Lviv, Ukraine
Topology : the science of objects which can be infinitely
distorted (totally different from Euclidian geometry)
Chemical Topology : mostly the synthesis and the study of
molecular systems whose graphs are non planar (i.e., which
can not be represented in a plane without crossing points)
Brevetoxin A or C60 are topologically trivial (sorry!)
Schlegel
diagram
a [2]catenane
Schill & Lüttringhaus could prepare
small amounts of such compounds
via elegant but low-yielding and
multistep synthetic routes (Angew.
Chem., 1964)
a [2]rotaxane
copper(I)-templated synthesis of a [2]catenane
"entwining"
gf
gf
"gathering and threading"
Dietrich-Buchecker et al., Tet. Lett., 1983
Dietrich-Buchecker et al., JACS, 1984
OH
(27%)
Dietrich-Buchecker et al., JACS, 1984
KCN
[Cu(CH3CN)4][PF6]
(100%)
Dietrich-Buchecker et al. (1983-84) and Pascard et al. (1985)
Synthesis of Catenanes : "template" methods
➪ Fraser Stoddart and co-workers : p-p stacking and H
bonds (1989)
➪ Chris Hunter : H bonding (1992)
➪ Fritz Vögtle et al. : H bonding (1992)
➪ Makoto Fujita et al. : kinetically labile Pd-N bonds and
hydrophobic interactions (1994)
... and, later on, many other outstanding research teams
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)
From catenane to molecular machines
Molecular machines : a very active research area
Catenanes and Rotaxanes are very
well adapted to large amplitude
motions : pirouetting of a ring
around an axis, translation of a ring
along an axis and many other
possible movements
Two examples of biologically essential molecular machines
ATP-synthase :
rotary motor
Kinesin "walking" on
a microtubule :
molecular shuttle
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
= Cu(II)
= Cu(I)
+e-0.06 V
minutes
A molecular "shuttle": the compound is set in motion by
modifying the acceptor-donor interaction
a rotaxane dimer is the ideal topology for interconverting a
streched structure
and a"muscle"
contracted (2000➠)
system
a synthetic
molecular
Maria Consuelo Jiménez (Chelo)...Christiane Dietrich-Buchecker
A chemically
molecular
machine
(2005 ➠) :
Towards driven
an artificial
molecular
press
from an adjustable receptor to a molecular press : a [3]rotaxane
a)
= bipy
= bipy
= Cu(I)
= Cu(I)
= guest molecule
= guest molecule
-
+
= Zn(II) porphyrin
= Zn(II) poprhyrin
b)
= M-30 like macrocycle
= coordinating
ring
= bulky stopper
= bulky
stopper
JACS, 2008 & 2009
molecular chaperones
encapsulation, folding and
release of proteins
Schematic drawing and structure of a complex between
GroEs (blue) and GroEL (green), including a cross-section
through the GroEL part.
the organic components of the [3]rotaxane
O
O
N
N
N
N
O
N
N
N
O
N Zn N
N
O
O
34
O
N
N
N
N
O
N
O
N
N
N
N
N
O
demetalation of the
[3]rotaxane
R
R
N
N
N Zn N
N Zn N
N
N
R
O
N
R
R
N N
N N
N N
N N
N N
N
O
R
N N
Cu
N
N
2+ , 2PF6-
R
R
Cu
N
N
N
N
N
O
O
OO
O
Cu...Cu ~ 8 to 8.5 Å
O O
O
N
O
O
O
O O
O
KCN
CH2Cl2/CH3CN/H2O
R
R
N
N Zn N
N Zn N
N
N
R
O
N
N
N
R
R
R
N N
N N
N N
N N
N N
N N
N
O
N
O O
N
N
N
O
O
O
R
R
N
O
N
N
O
O
O
O O
O
95%
R
R
N Zn N
R
R
guest
N
N
N
N
N Zn N
N
N
R
O
N
N
N
R
R
R
N N
N N
N N
N N
N
N
N
N
O
N
O
N
N
N
O
O
O
N
O
N
O
O
O
O
O
N
N
N
O
O
N
N
log Kass= 7.5 ± 0.2
log Kass= 6.0 ±
0.2
These values reflect both the adaptability of the [3]rotaxane host
and the respective basicities of the guests
R
R
N
N
N Zn N
N Zn N
N
N
R
O
N
N
N
R
R
R
N N
N N
N N
N N
N N
N N
Cu
Cu
N
O
2+ , 2PF6-
R
R
N
N
N
N
N
O
O
OO
O
O O
O
N
N
O
O
O
O O
O
N
N
N
log Kass= 6.8 ± 0.2
log Kass= 6.8 ± 0.2
destabilisation
stabilisation
free rotaxane :
log Kass= 7.5 ± 0.2
log Kass= 6.0 ± 0.2
Two-dimensional interlocking arrays (2005 ➠)
Topologically linked Protein Rings in the Bacteriophage HK97 Capsid
Wikoff, Liljas, Duda, Tsuruta, Hendrix and Johnson, Science, 2000
a natural chain-mail
a cyclic [2]rotaxane tetramer consisting of two
"filaments" and two bis-macrocycles
Jean-Paul Collin, Julien Frey, Valérie Heitz
and Christian Tock – 2006 ➠
the organic fragments
MeO
OMe
N
N
N
N
the two-chelate rod
O
O
O
O
O
N
N
N
O
O
N
N
N
O
O
O
O
O
the bis-macrocycle
copper(I)-induced threading of two bismacrocycles on two rods: a cyclic [4]rotaxane
2
4
2
= spacer
= bidentate chelate
= Cu(I)
Jean-Paul Collin, Julien Frey, Valérie Heitz, Efstathia
Sakellariou and Christian Tock
the threading reaction
O
O
O
MeO
2
MeO
O N
OMe
N
N
N
N
O
O
O
O
O
O
O
N
N
Cu
Cu
N N
N N
4PF6
4 Cu(CH3CN)4PF6
O
2
O
O
O
N
N
O
O
O
N
N
O
O
N
N
O
O
O
OMe
N
N N
N N
N N
N N
Cu
Cu
CH2Cl2 / CH3CN
7days / r.t.
MeO
O
N
N O
O
O
O
O
N
N O
O
O
O
95%
O
OMe
X-ray structure :
Kari Rissanen
(2008)
A two-porphyrin [4]rotaxane :
towards high-control molecular
receptors
from an adjustable receptor to a molecular press : a [4]rotaxane
Trapping
-
Releasing
a [4]rotaxane with 2 porphyrinic plates
preliminary study : the quadruple "gathering-andthreading" step
the axles :
synthesis of the porphyrinic component
(i) pyridine, 60 °C (45%); (ii) 1) Zn(OAc)2, CHCl3/MeOH, reflux; 2) EDTA,
CHCl3/MeOH/H2O, r.t., 24h (quant.).
quantitative copper(I)-driven formation of a [4]pseudorotaxane
R
R
R
R
R
R
24 covalent bonds
between the two
chelating fragments
quantitative
“click” chemistry affords the
real rotaxane
(95% yield for the quadruple
stoppering reaction!)
JACS, 2010
~45 Å
~50 Å
MW ~ 9,000
host-guest properties of the [4]rotaxane
(7.3)
(7.4)
(no "internal" complex)
(weak internal plus external)
(no "internal" complex)
Chemical structures of guests G1 to G5
(stability constants : logKs)
demetalation leads to a collapsed structure
G
Guest
double black arrow : Guest
: intramolecular interactions betwwen PZn and a Lewis base
(triazole) of the axis
J.-P. Collin, F. Durola, V. Heitz, F. Reviriego,
Y. Trolez, Angew. Chem. IE, 2010
removal of the 4 copper(I) atoms
O
N
N N
N
N
Cu
N N
N
N
N
N
N
N
N
N
N
N
Cu
N N
Ar
N
N Zn N
N Zn N
N
N
N
N
N
N
N
N
N
N
N N
Cu
N
N
KCN
KCN
N N
Cu
N
N
O
OO
O
O
O
O
O
Ar
Ar
Ar
N
N N
Ar
Ar
N
Ar
O
O
OO
O
Ar
N N
N
O
O
O
O
4+ . 4PF6-
O
O
O
O
O
O
O
O
O
N N
N
O
formation of a totally collapsed structure :
no complexation properties anymore!
O O
O
O
O
O O
O O ON
N
O
N
O
N
N
N
N
N
N O
N
N
N
N N
N
N N
N Ar
N
N Ar
N
Ar
O
N
N
N
N
N
Ar
Zn
Ar
N
N
Ar
N
N
Zn
N
N
N
N
N
Ar
N
N
Ar
N
N
N
N
N
O
N
N
N
N
N
N
O N
N
N
N
O
O
O
O
O
O O
O
O
O
O
O
a switchable receptor
The collapsed [4]rotaxane is totally unable to
complex an organic guest internally
G
Guest
the host-guest properties are switched on and off by
metalation or demetalation
J.-P. Collin, F. Durola, V. Heitz, F. Reviriego,
Y. Trolez, Angew. Chem. IE, 2010
Catenanes and Knots
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-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
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…Jack Beierle...Jean-Paul Collin
towards molecular muscles : Maria Consuelo Jiménez
(Chelo)...Christiane Dietrich-Buchecker
photochemically induced motions (Bologna): Nicola Armaroli...Vincenzo
Balzani...Lucia Flamigni...Francesco Barigelletti...Barbara Ventura
Two-dimensional threaded arrays and adaptable receptor
Tomás Kraus (Strasbourg and Prague), Milos Budesinsky, Josef Cvacka
(Prague)
Jean-Paul Collin*, Julien Frey, Valérie Heitz*, Efstathia Sakellariou, Christian
Tock, Fabien Durola, Yann Trolez, Stéphanie Durot, Valérie Sartor and Benoît
Champin
Bi-isoquinoline ligands and their complexes
Fabien Durola & Oliver Wenger, Pirmin Roesel, David Hanss,
Alexander Prikhod′ko, Jacques Lux
X-ray structures: André De Cian
Kari Rissanen et al. (Jyväskylä, Finland), Lydia Brelot (Strasbourg)
Université de Strasbourg and CNRS
European Communities and Région Alsace
Many, many thanks to our Russian friends:
Professors Aslan Tsivadze and Yulia Gorbunova
Professor Alexander Varnek
Dr Alexandre Martynov
The organisers of this nice Summer School
Professor Volodymyr Novikov and his colleagues
Dr Olena Fedorova
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