Nanoscale Borromean rings

Accounts of Chemical Research

Volumn 38, Issue 1, 2005, Pages 1-9

  Cantrill, Stuart J ^a,b   Chichak, Kelly S ^a,c   Peters, Andrea J ^a,d,e,f   Stoddart, J Fraser ^a,g,h  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b UNIVERSITY OF BIRMINGHAM   (United Kingdom)

^c UNIVERSITY OF ALBERTA   (Canada)

^d UNIVERSITY OF WINNIPEG   (Canada)

^e SIMON FRASER UNIVERSITY   (Canada)

^f Stoddart Research Group

^g UNIVERSITY OF EDINBURGH   (United Kingdom)

^h CALIFORNIA NANOSYSTEMS INSTITUTE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

MACROCYCLIC COMPOUND;

ARTICLE; BORROMEAN RING; CHEMICAL STRUCTURE; NANOTECHNOLOGY; SUPRAMOLECULAR CHEMISTRY; SYNTHESIS; TECHNIQUE; TOPOGRAPHY;

2,2'-DIPYRIDYL; ALKANES; CRYSTALLOGRAPHY, X-RAY; CYCLIZATION; DNA; ETHERS; LIGANDS; MODELS, MOLECULAR; NANOTECHNOLOGY; NUCLEIC ACID CONFORMATION; QUATERNARY AMMONIUM COMPOUNDS;

EID: 12344290303     PISSN: 00014842     EISSN: None     Source Type: Journal    
DOI: 10.1021/ar040226x     Document Type: Article

References (63)

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2. Kékulé's dream reputedly involved visions of a serpent biting its own tail, the ancient Ouroboros, a symbol commonly associated with alchemy. For a glimpse of the debate on the origin of the benzene structure, see Rocke, A. J. Waking up to the Facts-The Cyclical Structure of Benzene is a Landmark Achievement in Chemistry-But Who Should Rightfully be Credited with its Discovery? Chem. Brit. 1993, 29, 401-402, and a reply: Noe, C. R.; Bader, A. Chem. Brit. 1993, 29, 402.
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17. There are, however, other considerations, such as the degree of twisting in either of the two rings, when contemplating two-ring links. In a simple two-crossing [2]catenane-link, both rings are flat. If, however, one of the rings contains a half-twist, then a doubly interlocked [2]catenane is obtained. See Nierengarten, J.-F.; Dietrich-Buchecker, C. O.; Sauvage, J.-P. Synthesis of a Doubly Interlocked [2]Catenane. J. Am. Chem. Soc. 1994, 776, 375-376. This interlocked molecule is one of the many elegant examples that Sauvage has introduced since 1983 into the arena of topological chemistry using metal ion templation. See Dietrich-Buchecker, C. O.; Sauvage, J.-P.; Kintzinger, J.-P. Une Nouvelle Famille de Molecules: Les Metallo-Catenanes. Tetrahedron Lett. 1983, 24, 5095-5098.
18. There are, however, other considerations, such as the degree of twisting in either of the two rings, when contemplating two-ring links. In a simple two-crossing [2]catenane-link, both rings are flat. If, however, one of the rings contains a half-twist, then a doubly interlocked [2]catenane is obtained. See Nierengarten, J.-F.; Dietrich-Buchecker, C. O.; Sauvage, J.-P. Synthesis of a Doubly Interlocked [2]Catenane. J. Am. Chem. Soc. 1994, 776, 375-376. This interlocked molecule is one of the many elegant examples that Sauvage has introduced since 1983 into the arena of topological chemistry using metal ion templation. See Dietrich-Buchecker, C. O.; Sauvage, J.-P.; Kintzinger, J.-P. Une Nouvelle Famille de Molecules: Les Metallo-Catenanes. Tetrahedron Lett. 1983, 24, 5095-5098.
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20. van Gulick, N. Theoretical Aspects of the Linked Ring Problem. New J. Chem. 1993, 77, 619-625. This manuscript was written in 1960 and circulated as a preprint after being rejected by Tetrahedron as "not being chemistry" before finally being published in 1993. For a commentary, see Walba, D. M. Preface to van Gulick Paper. New J. Chem. 1993, 77, 618.
21. For a cyclic [3]catenane, such as that depicted by structure III, there are four possible topological stereoisomers. In this two-dimensional representation, the crossing of any two rings is equivalent to one-half-turn of a helix. In this case, the sense of all three helices is right-handed, i.e., PPP. The structure in which all three helices are left-handed (MMM) is a nonsuperimposable mirror image of III; i.e., it is a topological enantiomer. A topological diastereoisomer of III is one in which the sense of only one of the helical crossings is reversed, i.e., the MMP isomer, which constitutes a second topologically enantiomeric pair with its nonsuperimposable mirror image, namely, the PPM isomer.
22. Cromwell, P. R.; Beltrami E.; Rampichini, M. The Borromean Rings. Math. Intelligencer 1998, 20, no. 1, 53-62. This article has been expanded and adapted into a webpage, see http:// www.liv.ac.uk/~spmr02/rings/index.html.
23. Although named after the Borromeo family, this linked symbol is also associated with other prominent Italian families of the period (for details, see ref 15). Most notable amongst these is the Medici family of Florence, whose connection with this imagery is immortalized in Botticelli's painting, Pallas and the Centaur. Finished in 1482, this piece of art, commissioned by Lorenzo di Piero de'Medici, otherwise known as Lorenzo the Magnificent, depicts Pallas (Athena) taming a centaur, a motif that is thought to be allegorical of wisdom triumphing over instinct. Significantly, the gown worn by Pallas is decorated with three- and four-component links, with the former akin to the Borromean rings, which were symbols of the Medici family. This painting now hangs in the Uffizi Gallery in Florence. We thank Joanne Wright in the Department of Fine Arts at the University of Nottingham for bringing this association to our attention.
24. Siegel, J. S. Chemical Topology and Interlocking Molecules. Science 2004, 304, 1256-1258.
25. Rings with the Borromean-link topology have been fashioned into logos of numerous organizations, including (i) the Ricordi Music Company, (ii) the Pisa Research Corporation, in which a Mobiüs strip is intertwined with the three-ring link, and (iii) the Ballantine Brewery of Newark, NJ. For a more comprehensive list, consult ref 15. Interestingly, it has been observed (Nickon, A.; Silversmith, E. F. Organic Chemistry-The Name Game; Pergamon Press: New York, 1987; pp 156-157) that, in the 1950s, students in Harvard's research laboratories would refer to "ballantine compounds" when describing Borromean-ring structures.
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32. A rotaxane is a molecule comprised of a linear dumbbell-shaped component-bearing bulky end groups-around which one or more macrocycles are trapped. Although remote from mathematical concepts such as topology-the molecular graph of a rotaxane is, without exception, planar (see ref 10b)-rotaxanes are usually associated with their interlocked brethren, i.e., catenanes, as a consequence of structural similarity exhibited by those two archetypal classes of mechanically-linked compounds. The first reported synthesis of a rotaxane appeared less than a decade after that announcing the first catenane, see Harrison, I. T.; Harrison, S. The Synthesis of a Stable Complex of a Macrocycle and a Threaded Chain. J. Am. Chem. Soc. 1967, 89, 5723-5724.
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36. Regardless of which pathway is chosen, the final step in the synthesis of any molecular expression of the Borromean link is the ring closure of the third ring. The nature of the intermediate that exists immediately prior to this post-assembly covalent modification may differ in a geometric sense; i.e., it may or may not incorporate a ring-in-ring motif, but the topology is the same and necessarily remains independent of the pathway, otherwise the product would not be the Borromean rings!
37. Herein, the term "ring-in-ring" describes a complex in which one macrocyclic component is threaded through another such that their mean planes are approximately perpendicular to each other. For examples of the more familiar "macrocycle-within-macrocycle" juxtaposition, in which the mean planes of the rings are roughly coincident, see (a) Kim, S.-Y.; Jung, I.-S.; Lee, E.; Kim, J.; Sakamoto, S.; Yamaguchi, K.; Kim, K. Macrocycles Within Macrocycles: Cyclen, Cyclam, and their Transition Metal Complexes Encapsulated in Cucurbit[8]uril. Angew. Chem., Int. Ed. 2001, 40, 2119-2121.
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40. Hubin, T. J.; Kolchinski, A. G.; Vance, A. L.; Busch, D. H. Template Control of Supramolecular Architecture. Adv. Supramol. Chem. 1999, 5, 237-357. Prior to this report, in partial satisfaction of UCLA doctoral degree requirements, one of us presented a not dissimilar ring-in-ring strategy. See Cantrill, S. J. The Synthesis of Borromean Rings. UCLA Original Research Proposal, December 15, 1998.
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55. Whereas the simplest Borromean link possesses 6 crossing points, Seeman's DNA Borromean rings have 18 crossings. The specific emblem of the Borromeo family is the first in a series of such links in which the number of crossings is a multiple of 6. This DNA congener, therefore, is the third in the series. For a discussion on this family of links, see Liang, C.; Mislow, K. On Borromean Links. J. Math. Chem. 1994, 76, 27-35.
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58. (a) Chichak, K. S.; Cantrill, S. J.; Pease, A. R.; Chiu, S.-H.; Cave, G. W. V.; Atwood, J. L.; Stoddart, J. F. Molecular Borromean Rings. Science 2004, 304, 1308-1312.
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63. For a metallic microstructure possessing the Borromean topology, see Wu, H.; Brittain, S.; Anderson, J.; Grzybowski, B.; Whitesides, S.; Whitesides, G. M. Fabrication of Topologically Complex Three-Dimensional Microstructures: Metallic Microknots. J. Am. Chem. Soc. 2000, 722, 12691-12699.