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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)

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slide2

Topology : the science of objects which can be infinitely distorted (totally differentfrom 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

slide3

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)

slide5

gf

gf

Dietrich-Buchecker et al., Tet. Lett., 1983

"entwining"

"gathering and threading"

slide7

(27%)

OH

Dietrich-Buchecker et al., JACS, 1984

slide8

KCN

[Cu(CH3CN)4][PF6]

(100%)

Dietrich-Buchecker et al. (1983-84) and Pascard et al. (1985)

slide9

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

slide10

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)

slide11

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

slide12

Two examples of biologically essential molecular machines

ATP-synthase : rotary motor

Kinesin "walking" on a microtubule :

molecular shuttle

slide13

= Cu(II)

= Cu(I)

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

+e-

-0.06 V

slide15

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

a synthetic molecular muscle 2000

a synthetic molecular "muscle" (2000➠)

Maria Consuelo Jiménez (Chelo)...Christiane Dietrich-Buchecker

slide17

a)

=bipy

=Cu(I)

=guest molecule

-

+

=Zn(II) poprhyrin

b)

=M-30 like macrocycle

= bulky stopper

A chemically driven molecular machine (2005 ➠) :

from an adjustable receptor to a molecular press : a [3]rotaxane

Towards an artificial molecular press

= bipy

= Cu(I)

= guest molecule

= Zn(II) porphyrin

= coordinating ring

= bulky stopper

JACS, 2008 & 2009

slide18

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.

slide20

demetalation of the [3]rotaxane

Cu...Cu ~ 8 to 8.5 Å

KCN

CH2Cl2/CH3CN/H2O

95%

slide21

guest

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

slide22

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

slide24

Topologically linked Protein Rings in the Bacteriophage HK97 Capsid

Wikoff, Liljas, Duda, Tsuruta, Hendrix and Johnson, Science, 2000

a natural chain-mail

slide25

a cyclic [2]rotaxane tetramer consisting of two "filaments" and two bis-macrocycles

Jean-Paul Collin, Julien Frey, Valérie Heitz and Christian Tock – 2006 ➠

slide26

the organic fragments

the two-chelate rod

the bis-macrocycle

slide27

= spacer

= bidentate chelate

= Cu(I)

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

slide28

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P

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u

(

C

H

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N

)

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N

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l

/

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7

d

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/

r

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the threading reaction

95%

slide31

Trapping

-

Releasing

from an adjustable receptor to a molecular press : a [4]rotaxane

from an adjustable receptor to a molecular press : a [4]rotaxane

slide35

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.).

slide38

“click” chemistry affords the real rotaxane

(95% yield for the quadruple stoppering reaction!)

slide40

~45 Å

~50 Å

MW ~ 9,000

slide41

host-guest properties of the [4]rotaxane

(weak internal plus external)

(7.3)

(7.4)

(no "internal" complex)

(no "internal" complex)

Chemical structures of guests G1 to G5

(stability constants : logKs)

slide42

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

slide44

formation of a totally collapsed structure :

no complexation properties anymore!

slide45

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

slide46

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

Catenanes and Knots

X-ray structures

Claudine Pascard…Michèle Césario (Gif-sur-Yvette)

Jean-Fischer…André De Cian…Nathalie Gruber

…Richard Welter (Strasbourg)

slide47

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
slide48

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)

slide49

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