Pr

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catenane
rotaxane
knot
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Schill and coworkers
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Topologically linked Protein Rings in the
Bacteriophage HK97 Capsid Wikoff, Liljas, Duda,
Tsuruta, Hendrix and Johnson, Science, 2000
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a natural "coat of mail"
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Dietrich-Buchecker et al., JACS, 1984
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synthesis of catenanes following a one-step
strategy
entwining of two open-chain fragments around
Cu(I) followed by Ring-Closing Metathesis (RCM)
of terminal olefins
92 yield (isolated)
Grubbs Weck / Mohr
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using 27-membered rings as peripheral units,
multiring interlocking systems could be obtained
132-memberd central ring
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Towards Rotary Motors

• A copper-containing catenane whose rings rotate
  between two positions without direction control

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ATP synthase is the most important rotaxane of
Nature
Rastogi Girvin, Nature, 1999
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rotation of a ring within another ring (no
directionality) use of the Cu(II)/Cu(I) couple
Livoreil et al., 1994
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-e-
seconds
Livoreil et al., 1994
minutes
e-
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a 2catenane with three distinct situations
rotation of both rings within the other ring
each ring incorporates both a bi- and a
tri-dentate coordinating unit
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molecular shuttles gliding of a ring along the
axle on which it is threaded
signal 1
signal 2
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Science, Vol. 294, 21 December 2001, p.2442
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(A) Molecular drawing of the bistable 2catenane
used in this work. The voltage-driven
circumrotation of co-conformer A0 to
co-conformer B is the basis of the device.
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(B) Proposed mechanism for the operation of the
device. Co-conformer A0 represents both the
ground-state structure of the 2catenane and the
switch open state of the device. When the
2catenane is oxidized, the TTF groups (green)
are ionized. The coconformer B is formed. When
the voltage is reduced to a near-zero bias, the
co-conformer B0 is formed, and this represents
the switch closed state of the device. Partial
reduction of the cyclophane (2 V) is necessary
to regenerate the A0 co-conformer. The reduced
co-conformer AB is indicated with an unknown
oxidation state.
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towards a synthetic molecular "muscle"

• a copper-complexed rotaxane dimer whose overall
  length can be modified by a chemical signal

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Maria Consuelo Jiménez (Chelo) and Christiane
Dietrich-Buchecker
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the key step formation of the rotaxane dimer
?
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formation of the rotaxane dimer
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X-ray structure of the doubly threaded species
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the two states of the "muscle"
extended
85 Å
Zn2
contracted
65 Å
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Synthesis and Coordination Chemistry Laboratoir
e de Chimie Organo-Minérale (Strasbourg) Christian
e 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 HwangChristine Hamann
Catenanes and Knots
X-ray structures
Claudine Pascard et al. (Gif-sur-Yvette) Jean-Fisc
herAndré De CianNathalie Gruber Richard Welter
(Strasbourg)
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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 oscillation/rotation of an axle inside a
wheel  Laurence Raehm...Jean-Marc Kern towards
molecular muscles  Maria Consuelo Jiménez
(Chelo)...Christiane Dietrich-Buchecker photochem
ically induced motions (Bologna)  Nicola
Armaroli...Vincenzo Balzani...Lucia
Flamigni...Barbara Ventura
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