0000000001303219
AUTHOR
J.-p. Collin
Synthesis of [5]Rotaxanes Containing Bi- and Tridentate Coordination Sites in the Axis
A new example of a linear [5]rotaxane has been synthesized by using the traditional "gathering-and-threading" approach but based on an unusual axle incorporating a symmetrical bis(bidentate) chelating fragment built on a 4,7-phenanthroline core. The stoppering reaction is particularly noteworthy since, instead of using a trivial bulky stopper as precursor to the blocking group, two semistoppered copper-complexed [2]pseudorotaxanes (namely [2]semirotaxanes) are used, which leads to the desired [5]rotaxane in good yield. The efficiency of the method relies on the use of "click" chemistry, with its very mild conditions, and on the protection by a transition-metal (copper(I)) of the various coo…
Cyclic [2]Pseudorotaxane Tetramers Consisting of Two Rigid Rods Threaded through Two Bis-Macrocycles: Copper(I)-Templated Synthesis and X-ray Structure Studies
Variously substituted coordinating rigid rods have been synthesized which incorporate a central 4,7-phenanthroline nucleus attached to two 2-pyridyl groups via its 3 and 8 positions, so as to yield bis-bidentate chelates, the two-coordinating axes of the chelates being parallel to one another. Regardless of the nature of the substituents borne by the rods, the copper(I)-induced threading reaction of two such rods through the rings of two bis-macrocycles affords in a quantitative yield the 4-copper(I) threaded assembly. The [2]pseudorotaxane tetramers thus obtained have been fully characterized in solution and, for one of them, an X-ray structure could be obtained, confirming the threaded na…
[3]Rotaxanes and [3]pseudorotaxanes with a rigid two-bidentate chelate axle threaded through two coordinating rings
New [3]rotaxanes and [3]pseudorotaxanes have been synthesised using the “gathering and threading” effect of copper(I). By using click chemistry as the “stoppering” reaction, a good yield of the [3]rotaxane was obtained, either as a dicopper complex or as a metal-free compound after demetallation. The axle contains a central rigid aromatic block incorporating two bidentate chelates, and the threaded macrocycles are 30-membered rings. A model dicopper(I) [3]pseudorotaxane whose axle was end-functionalised by triisopropylsilyl groups could be crystallised and studied by X-ray diffraction. A particularly attractive structure was obtained showing a “slanted” geometry for the two rings and the ax…
CCDC 189634: Experimental Crystal Structure Determination
Related Article: D.Pomeranc, D.Jouvenot, J.-C.Chambron, J.-P.Collin, V.Heitz, J.-P.Sauvage|2003|Chem.-Eur.J.|9|4247|doi:10.1002/chem.200304716
CCDC 200198: Experimental Crystal Structure Determination
Related Article: D.Pomeranc, D.Jouvenot, J.-C.Chambron, J.-P.Collin, V.Heitz, J.-P.Sauvage|2003|Chem.-Eur.J.|9|4247|doi:10.1002/chem.200304716
CCDC 733684: Experimental Crystal Structure Determination
Related Article: J.-P.Collin, J.-P.Sauvage, Y.Trolez, K.Rissanen|2009|New J.Chem.|33|2148|doi:10.1039/b9nj00278b
CCDC 781080: Experimental Crystal Structure Determination
Related Article: J.-P.Collin, S.Durot, M.Keller, J.-S.Sauvage, Y.Trolez, M.Cetina, K.Rissanen|2011|Chem.-Eur.J.|17|947|doi:10.1002/chem.201002220