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A [2]Catenane and a [2]Rotaxane as Prototypes of Topological and Euclidean Molecular “Rubber Gloves”
Author(s) -
Chambron JeanClaude,
Sauvage JeanPierre,
Mislow Kurt,
De Cian André,
Fischer Jean
Publication year - 2001
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20011001)7:19<4085::aid-chem4085>3.0.co;2-m
Subject(s) - catenane , rotaxane , molecule , chemistry , stereochemistry , crystallography , topology (electrical circuits) , combinatorics , supramolecular chemistry , mathematics , organic chemistry
A [2]catenane and a [2]rotaxane have been prepared from a C 2 ‐symmetric, 2,9‐diphenyl‐1,10‐phenanthroline‐based (dpp‐based) macrocycle incorporating a 1,5‐dioxynaphthalene subunit by means of the transition metal templated technique. In the case of the catenane, this macrocycle is interlocked with a dpp‐based macrocycle that is oriented through the location of a p ‐tolyl substituent in the 4‐position of the phenanthroline subunit. In the case of the rotaxane, the C 2 ‐symmetric macrocycle is threaded onto an oriented, dumbbell‐shaped molecule, based on the same 4‐ p ‐tolyl‐1,10‐phenanthroline subunit, which bears tetraarylmethane stoppers. Both species are chemically achiral molecules, yet they are composed entirely of asymmetric, mirror‐image conformations. Conformational enantiomerization processes therefore take place exclusively by chiral pathways, conferring on these molecules the “rubber glove” property. However, while the molecular graph (constitutional formula) of the [2]rotaxane can be deformed into a planar and, hence, rigidly achiral representation, a feature shared by a few other compounds in the literature that have been characterized as “Euclidean rubber gloves”, the molecular graph of the [2]catenane cannot be deformed in this way. It therefore has the unique property of being a chemically achiral “topological rubber glove”.