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3rd International Summer School Supramolecular Systems in Chemistry and Biology Lviv, Ukraine.

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Presentation on theme: "3rd International Summer School Supramolecular Systems in Chemistry and Biology Lviv, Ukraine."— Presentation transcript:

1 3rd International Summer School Supramolecular Systems in Chemistry and Biology Lviv, Ukraine

2 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 C 60 are topologically trivial (sorry!) Schlegel diagram

3 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)

4 copper(I)-templated synthesis of a [2]catenane

5 Dietrich-Buchecker et al., Tet. Lett., 1983 gf "entwining" "gathering and threading"

6 Dietrich-Buchecker et al., JACS, 1984

7 OH (27%) Dietrich-Buchecker et al., JACS, 1984

8 (100%) Dietrich-Buchecker et al. ( ) and Pascard et al. (1985) KCN [Cu(CH 3 CN) 4 ][PF 6 ]

9 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

10 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

11 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

12 Two examples of biologically essential molecular machines Kinesin "walking" on a microtubule : molecular shuttle ATP-synthase : rotary motor

13 -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) V V


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

16 a synthetic molecular "muscle" (2000 ) Maria Consuelo Jiménez (Chelo)...Christiane Dietrich-Buchecker

17 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

18 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

19 the organic components of the [3]rotaxane

20 demetalation of the [3]rotaxane KCN CH 2 Cl 2 /CH 3 CN/H 2 O 95% Cu...Cu ~ 8 to 8.5 Å

21 guest These values reflect both the adaptability of the [3]rotaxane host and the respective basicities of the guests log K ass = 7.5 ± 0.2 log K ass = 6.0 ± 0.2

22 log K ass = 6.8 ± 0.2 destabilisationstabilisation free rotaxane : log K ass = 7.5 ± 0.2 log K ass = 6.0 ± 0.2

23 Two-dimensional interlocking arrays (2005 )

24 a natural chain-mail Topologically linked Protein Rings in the Bacteriophage HK97 Capsid Wikoff, Liljas, Duda, Tsuruta, Hendrix and Johnson, Science, 2000

25 a cyclic [2]rotaxane tetramer consisting of two "filaments" and two bis-macrocycles Jean-Paul Collin, Julien Frey, Valérie Heitz and Christian Tock – 2006

26 the bis-macrocycle the two-chelate rod the organic fragments

27 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

28 95% the threading reaction

29 X-ray structure : Kari Rissanen (2008)

30 A two-porphyrin [4]rotaxane : towards high-control molecular receptors

31 - Trapping Releasing from an adjustable receptor to a molecular press : a [4]rotaxane

32 a [4]rotaxane with 2 porphyrinic plates

33 preliminary study : the quadruple "gathering-and- threading" step

34 the axles :

35 (i) pyridine, 60 °C (45%); (ii) 1) Zn(OAc) 2, CHCl 3 /MeOH, reflux; 2) EDTA, CHCl 3 /MeOH/H 2 O, r.t., 24h (quant.). synthesis of the porphyrinic component

36 R R R R R R quantitative copper(I)-driven formation of a [4]pseudorotaxane

37 24 covalent bonds between the two chelating fragments quantitative

38 click chemistry affords the real rotaxane (95% yield for the quadruple stoppering reaction!)

39 JACS, 2010

40 ~50 Å ~45 Å MW ~ 9,000

41 Chemical structures of guests G1 to G5 (stability constants : logKs) (7.4) (7.3) (no "internal" complex) (weak internal plus external) host-guest properties of the [4]rotaxane

42 demetalation leads to a collapsed structure Guest G 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

43 removal of the 4 copper(I) atoms KCN

44 formation of a totally collapsed structure : no complexation properties anymore!

45 The collapsed [4]rotaxane is totally unable to complex an organic guest internally Guest G 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

46 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 Claudine Pascard…Michèle Césario (Gif-sur-Yvette) Jean-Fischer…André De Cian…Nathalie Gruber …Richard Welter (Strasbourg) X-ray structures

47 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

48 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 Prikhodko, Jacques Lux X-ray structures: André De Cian Kari Rissanen et al. (Jyväskylä, Finland), Lydia Brelot (Strasbourg)

49 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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