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153
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84891030513
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Numbers in square brackets preceding the names of interlocked compounds indicate the number of mechanically interlocked species, e.g. a [2]rotaxane consists of one macrocycle and one thread component mechanically interlocked; two macrocycles both locked around the same thread would constitute a [3]rotaxane.
-
Numbers in square brackets preceding the names of interlocked compounds indicate the number of mechanically interlocked species, e.g. a [2]rotaxane consists of one macrocycle and one thread component mechanically interlocked; two macrocycles both locked around the same thread would constitute a [3]rotaxane.
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154
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0000766196
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The concept of constructing a molecular catenane was first postulated by Willstät-ters before 1912 (see refs. [59a, 59b]). The first statistical synthesis of a catenane was achieved by Wasserman in 1960:
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The concept of constructing a molecular catenane was first postulated by Willstät-ters before 1912 (see refs. [59a, 59b]). The first statistical synthesis of a catenane was achieved by Wasserman in 1960: E. Wasserman, J. Am. Chem. Soc. 1960, 82, 4433-4434;
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and the first directed synthesis by Lüttringhaus and Schill in 1964:
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and the first directed synthesis by Lüttringhaus and Schill in 1964: G. Schill, A. Lüttringhaus, Angew. Chem. Int. Ed. Engl. 1964, 3, 546-547.
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The first rotaxane was synthesized by Harrison and Harrison in 1967:
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The first rotaxane was synthesized by Harrison and Harrison in 1967: I. T. Harrison, S. Harrison, J. Am. Chem. Soc. 1967, 89, 5723-5724;
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181
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84891028321
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Metal-coordinated catenanes are sometimes known as catenates. Demetallation to give the uncomplexed, but still interlocked, ligands gives a catenand. No similar nomenclature is used for metal-coordinated rotaxane-like structures however, which are named as their organic counterparts. In recent times, the use of the terms "catenate" and "catenand" has largely been superseded in the literature by the more general "catenane".
-
Metal-coordinated catenanes are sometimes known as catenates. Demetallation to give the uncomplexed, but still interlocked, ligands gives a catenand. No similar nomenclature is used for metal-coordinated rotaxane-like structures however, which are named as their organic counterparts. In recent times, the use of the terms "catenate" and "catenand" has largely been superseded in the literature by the more general "catenane".
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185
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0029849783
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This previously inaccessible species was obtained by trapping round an acyclic, stoppered benzylic amide thread to create a [2]rotaxane, followed by controlled cleavage of the thread and resultant de-threading:
-
This previously inaccessible species was obtained by trapping round an acyclic, stoppered benzylic amide thread to create a [2]rotaxane, followed by controlled cleavage of the thread and resultant de-threading: A. G. Johnston, D. A. Leigh, A. Murphy, J. P. Smart, M. D. Deegan, J. Am. Chem. Soc. 1996, 118, 10662-10663.
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191
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84990151906
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P. R. Ashton, T. T. Goodnow, A. E. Kaifer, M. V. Reddington, A. M. Z. Slawin, N. Spencer, J. F. Stoddart, C. Vicent, D. J. Williams, Angew. Chem. Int. Ed. Engl. 1989, 28, 1396-1399.
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192
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P. R. Ashton, C. L. Brown, E. J. T. Chrystal, K. P. Parry, M. Pietraszkiewicz, N. Spencer, J. F. Stoddart, Angew. Chem. Int. Ed. Engl. 1991, 30, 1042-1045.
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193
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84891001455
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The distal isomer may still be involved transiently in the circumvolution mechanism.
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The distal isomer may still be involved transiently in the circumvolution mechanism.
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194
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33748221558
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For further studies on the effect of structure on the dynamic properties of similar catenanes, see
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For further studies on the effect of structure on the dynamic properties of similar catenanes, see: D. B. Amabilino, P. R. Ashton, M. S. Tolley, J. F. Stoddart, D. J. Williams, Angew. Chem. Int. Ed. Engl. 1993, 32, 1297-1301;
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P. R. Ashton, M. A. Blower, S. Iqbal, C. H. McLean, J. F. Stoddart, M. S. Tolley, D. J. Williams, Synlett 1994, 1059-1062;
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D. B. Amabilino, P. L. Anelli, P. R. Ashton, G. R. Brown, E. Cordova, L. A. Godinez, W. Hayes, A. E. Kaifer, D. Philp, A. M. Z. Slawin, N. Spencer, J. F. Stoddart, M. S. Tolley, D. J. Williams, J. Am. Chem. Soc. 1995, 117, 11142-11170;
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With the notable exception of the earliest statistically constructed [2]rotaxanes (see refs. [64c, 64d]), there are very few examples of rotaxanes without any recognition elements in the thread, see however:
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With the notable exception of the earliest statistically constructed [2]rotaxanes (see refs. [64c, 64d]), there are very few examples of rotaxanes without any recognition elements in the thread, see however: C. Heim, A. Affeld, M. Nieger, F. Vögtle, Helv. Chim. Acta 1999, 82, 746-759;
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Shuttle 41 also shows a certain degree of electrochemical switching in the deproto-nated state when electrochemical reduction of the bipyridinium unit causes movement of the macrocycle back towards the amine moiety. In this state however, the electron-rich macrocycle has no significant favorable interactions with the thread and its position is not well-defined, see ref. [99a].
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Shuttle 41 also shows a certain degree of electrochemical switching in the deproto-nated state when electrochemical reduction of the bipyridinium unit causes movement of the macrocycle back towards the amine moiety. In this state however, the electron-rich macrocycle has no significant favorable interactions with the thread and its position is not well-defined, see ref. [99a].
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Heat has been used to effect cis-trans isomerization in 46 resulting in a concomitant net change of position of the ring (see ref. [108]), while a temperature increase has also been used to overcome a significant kinetic barrier to shuttling, following a chemical change in a kineti-cally stable pseudorotaxane (see Ref. [58b]). In neither of these cases is the process reversible on cooling the material without some other stimulus being applied.
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Heat has been used to effect cis-trans isomerization in 46 resulting in a concomitant net change of position of the ring (see ref. [108]), while a temperature increase has also been used to overcome a significant kinetic barrier to shuttling, following a chemical change in a kineti-cally stable pseudorotaxane (see Ref. [58b]). In neither of these cases is the process reversible on cooling the material without some other stimulus being applied.
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12) possible C-C rotamers and a significant number of these degrees of freedom must be lost upon forming the dodec-Z-47 structure.
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12) possible C-C rotamers and a significant number of these degrees of freedom must be lost upon forming the dodec-Z-47 structure.
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The use of terms such as "all or nothing" or "quantitative" are inappropriate descriptions of an equilibrium.
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It has recently been suggested that unidirectional pirouetting could result from simply derivatizing rotaxanes with chiral or knotted stoppers (see:, As discussed in Section 7.2, this is incorrect. Directional rotation can only result from an external energy source being used to drive the system temporarily away from equilibrium.
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