title: Copper(I)-assembled [3]rotaxane whose two rings act as flapping wings.
abstract: A new copper-complexed [3]rotaxane consisting of two coordinating 30-membered rings threaded by a two-binding-site axis has been prepared in good yield from relatively simple organic fragments. The main specificity of the system originates from the stoppering reaction, based on "click" chemistry, and thus from the presence of two triazole groups at positions next to the bidentate chelates of the axis central part. The geometry of the coordinating atoms belonging to the axis is such that the triazole groups can either be part of the coordinating fragments when the metal center is 5-coordinate or be not at all involved in coordination to the metal when the latter is 4-coordinate. To be more specific, when the two complexed metal centers are monovalent copper(I) centers, the triazoles are not included in the metal coordination sphere, whereas when the metal centers are Cu(II) or Zn(2+), the triazole groups are bound to the metals. This is easily explained by the fact that Cu(I) is preferably 4-coordinate and Cu(II) and Zn(2+) are 5-coordinate. The interconversion between both situations (4- or 5-coordinate) can be quantitatively induced by metal exchange (Cu(I)/Zn(2+)) or by a redox process (Cu(II)/Cu(I)). It leads to important geometrical changes and in particular to a strong modification of the angle between the two rings. As a consequence, the two threaded rings undergo a motion which is reminiscent of a wing-flapping movement similar to that of birds. This flapping motion is fast and quantitative. It should lead to new functional molecular machines in the future.
authors.affiliation: Laboratoire de Chimie Organo-Minérale, Institut de Chimie, Université de Strasbourg-CNRS/UMR7177, 4 rue Blaise Pascal, 67070 Strasbourg Cedex, France.
authors.forename: Antoine
authors.initials: A
authors.lastname: Joosten
authors.forename: Yann
authors.initials: Y
authors.lastname: Trolez
authors.forename: Jean-Paul
authors.initials: JP
authors.lastname: Collin
authors.forename: Valérie
authors.initials: V
authors.lastname: Heitz
authors.forename: Jean-Pierre
authors.initials: JP
authors.lastname: Sauvage