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3rd International Summer School “Supramolecular Systems in Chemistry and Biology” Lviv, Ukraine
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Transcript of 3rd International Summer School “Supramolecular Systems in Chemistry and Biology” Lviv, Ukraine
3rd International Summer School “Supramolecular Systems in
Chemistry andBiology”
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
a [2]rotaxane
Schill & Lüttringhaus could prepare small amounts of such compounds
via elegant but low-yielding and multistep synthetic routes (Angew.
Chem., 1964)
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%)
Dietrich-Buchecker et al., JACS, 1984
(100%)
Dietrich-Buchecker et al. (1983-84) and Pascard et al. (1985)
KCN
[Cu(CH3CN)4][PF6]
Synthesis of Catenanes : "template" methods
➪ Fraser Stoddart and co-workers : 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
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
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
Kinesin "walking" on a microtubule :
molecular shuttle
ATP-synthase : rotary motor
-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
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 contracted systema synthetic molecular "muscle" (2000 )➠
Maria Consuelo Jiménez (Chelo)...Christiane Dietrich-Buchecker
Towards an artificial molecular press
- +
a)
b)
= Cu(I)
= bipy
= guest molecule
= Zn(II) poprhyrin
= M-30 like macrocycle
= bulky stopper
= bipy
= Cu(I)
= guest molecule
= Zn(II) porphyrin
= coordinating ring
= bulky stopper
A chemically driven molecular machine (2005 ) : ➠from an adjustable receptor to a molecular press : a [3]rotaxane
JACS, 2008 & 2009
Schematic drawing and structure of a complex between GroEs (blue) and GroEL (green), including a cross-section
through the GroEL part.
molecular chaperones
encapsulation, folding and release of proteins
NN
O
O
OO
OO
NN
NN N
NNNZn
34
the organic components of the [3]rotaxane
N
NOO
ON
NN
ONNN
N
N
demetalation of the [3]rotaxane
KCN
CH2Cl2/CH3CN/H2O
95%
Cu...Cu ~ 8 to 8.5 Å
N
NOO
O NNN
ONNN
N N
O
N
N
N
N
R R
R R
N N
N N
Zn
OO
OO
N
N N
O
N
N
N
N
R R
R R
N N
N N
Zn
OO
OO
N
N
N N
OO
N
N
N
N
R R
R R
N N
N N
Zn
N
OO
OO
N
N N
OO
N
N
N
N
R R
R R
N N
N N
Zn
N
OO
OO
OO
2+ , 2PF6-
O NNN
ONNN
Cu Cu
NN
N N
N
NOO
ON
NN
ONNN
N N
O
N
N
N
N
R R
R R
N N
N N
Zn
OO
OO
N
N N
O
N
N
N
N
R R
R R
N N
N N
Zn
OO
OO
N
N N
guest
These values reflect both the adaptability of the [3]rotaxane host
and the respective basicities of the guests
log Kass= 7.5 ± 0.2 log Kass= 6.0 ± 0.2
NN
N N
log Kass= 6.8 ± 0.2 log Kass= 6.8 ± 0.2
N
N N
OO
N
N
N
N
R R
R R
N N
N N
Zn
N
OO
OO
N
N N
OO
N
N
N
N
R R
R R
N N
N N
Zn
N
OO
OO
OO
2+ , 2PF6-
O NNN
ONNN
Cu Cu
destabilisation stabilisation
free rotaxane : log Kass= 7.5 ± 0.2 log Kass= 6.0 ± 0.2
Two-dimensional interlocking arrays (2005 )➠
a natural chain-mail
Topologically linked Protein Rings in the Bacteriophage HK97 Capsid
Wikoff, Liljas, Duda, Tsuruta, Hendrix and Johnson, Science, 2000
a cyclic [2]rotaxane tetramer consisting of two
"filaments" and two bis-macrocycles
Jean-Paul Collin, Julien Frey, Valérie Heitz and Christian Tock – 2006 ➠
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
N NN NMeO OMe
NN NNOMeMeO
N
O
OO
N
OO
N
O
OO
N
OO
N N
N
O
OO
N
OO
N
OO
N
OO
N N
O O
O
Cu Cu
CuCu
4PF6
95%
the threading reaction
N NN NMeO OMe
N
OOO
NO
O N
O OO
NO
O
N
N
O
O
4 Cu(CH3CN)4PF6
CH2Cl2 / CH3CN
2
2 7 days / r.t.
X-ray structure : Kari Rissanen
(2008)
A two-porphyrin [4]rotaxane : towards high-control molecular
receptors
-
Trapping
Releasing
from an adjustable receptor to a molecular press : a [4]rotaxanefrom an adjustable receptor to a molecular press : a [4]rotaxane
a [4]rotaxane with 2 porphyrinic plates
preliminary study : the quadruple "gathering-and-threading" step
the axles :
(i) pyridine, 60 °C (45%); (ii) 1) Zn(OAc)2, CHCl3/MeOH, reflux; 2) EDTA, CHCl3/MeOH/H2O, r.t., 24h (quant.).
synthesis of the porphyrinic component
RR
R
RR
R
quantitative copper(I)-driven formation of a [4]pseudorotaxane
24 covalent bonds between the two
chelating fragments
quantitative
“click” chemistry affords the real rotaxane
(95% yield for the quadruple stoppering reaction!)
JACS, 2010
~50 Å
~45 Å
MW ~ 9,000
Chemical structures of guests G1 to G5
(stability constants : logKs)
(7.4) (7.3)
(no "internal" complex) (no "internal" complex)
(weak internal plus external)
host-guest properties of the [4]rotaxane
demetalation leads to a collapsed structure
GuestG
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
NN NN
NN
OO
OOOO
N
N N
N
NN
O O
NN
OO
OOOO
CuCu
NN NN
NN
OO
OOOO
N
N N
N
NN
O O
NN
OO
OOOO
CuCu
N
N
N
N
N N
NN
N N
NN
Zn
ArAr
ArArN
N
N
N
N N
NN
N N
NN
Zn
ArAr
ArAr
4+ . 4PF6-
KCN
removal of the 4 copper(I) atoms
KCN
ON
O
N
NN
N
N N
NN
NN
NN
NN
NN
NN
NN
Zn
O
O
O
OO
O
Ar
Ar
Ar
Ar
O
N
N
O
NNN
O
N N
NN
NN
NN
NN
NN
NN
NN
Zn
O
O
O
O
O
OO
O
O
O
Ar
Ar
Ar
Ar
NN
N
NNN N
O
OO
O
O NO
N
N
O
formation of a totally collapsed structure :no complexation properties anymore!
The collapsed [4]rotaxane is totally unable to complex an organic guest internally
GuestG
a switchable receptor
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
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 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…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