Strong and Selective Anion Binding within the Central Cavity of Molecular Knots and Links

Journal of the American Chemical Society

Volumn 137, Issue 31, 2015, Pages 9812-9815

  Ayme, Jean François ^a   Beves, Jonathon E ^a   Campbell, Christopher J ^a   Gil Ramírez, Guzmán ^a   Leigh, David A ^a   Stephens, Alexander J ^a  

^a UNIVERSITY OF MANCHESTER   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

HYDROGEN BONDS; NEGATIVE IONS; SALTS; SCAFFOLDS;

ANION BINDING; CHLORIDE IONS; HALIDE ANIONS; HOST MOLECULES; HYDROGEN BONDING INTERACTIONS; MOLECULAR KNOTS; SILVER SALTS; [2]CATENANES;

IONS;

ACETONITRILE; CATENANE; CHLORIDE ION; FERROUS ION; HALIDE; SILVER;

ARTICLE; BINDING AFFINITY; CRYSTAL STRUCTURE; HYDROGEN BOND; SYNTHESIS;

EID: 84939226109     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/jacs.5b06340     Document Type: Article

References (66)

1. Hasenknopf, B.; Lehn, J.-M.; Kneisel, B. O.; Baum, G.; Fenske, D. Angew. Chem., Int. Ed. Engl. 1996, 35, 1838 10.1002/anie.199618381
2. Hasenknopf, B.; Lehn, J.-M.; Boumediene, N.; Dupont-Gervais, A.; Van Dorsselaer, A.; Kneisel, B.; Fenske, D. J. Am. Chem. Soc. 1997, 119, 10956 10.1021/ja971204r
3. Hasenknopf, B.; Lehn, J.-M.; Boumediene, N.; Leize, E.; Van Dorsselaer, A. Angew. Chem., Int. Ed. 1998, 37, 3265 10.1002/(SICI)1521-3773(19981217)37:23<3265::AID-ANIE3265>3.3.CO;2-2
4. Dietrich-Buchecker, C.; Colasson, B. X.; Sauvage, J.-P. Top. Curr. Chem. 2005, 249, 261 10.1007/b104331
5. Lukin, O.; Vögtle, F. Angew. Chem., Int. Ed. 2005, 44, 1456 10.1002/anie.200460312
6. Fenlon, E. E. Eur. J. Org. Chem. 2008, 2008, 5023 10.1002/ejoc.200800578
7. Beves, J. E.; Blight, B. A.; Campbell, C. J.; Leigh, D. A.; McBurney, R. T. Angew. Chem., Int. Ed. 2011, 50, 9260 10.1002/anie.201007963
8. Forgan, R. S.; Sauvage, J.-P.; Stoddart, J. F. Chem. Rev. 2011, 111, 5434 10.1021/cr200034u
9. Amabilino, D. B.; Sauvage, J.-P. Top. Curr. Chem. 2012, 323, 107 10.1007/128-2011-292
10. Ayme, J.-F.; Beves, J. E.; Campbell, C. J.; Leigh, D. A. Chem. Soc. Rev. 2013, 42, 1700 10.1039/C2CS35229J
11. Gil-Ramírez, G.; Leigh, D. A.; Stephens, A. J. Angew. Chem., Int. Ed. 2015, 54, 6110 10.1002/anie.201411619
12. Beves, J. E.; Campbell, C. J.; Leigh, D. A.; Pritchard, R. G. Angew. Chem., Int. Ed. 2013, 52, 6464 10.1002/anie.201302634
13. Ayme, J.-F.; Beves, J. E.; Campbell, C. J.; Leigh, D. A. Angew. Chem., Int. Ed. 2014, 53, 7823 10.1002/anie.201404270
14. Ayme, J.-F.; Beves, J. E.; Leigh, D. A.; McBurney, R. T.; Rissanen, K.; Schultz, D. Nat. Chem. 2011, 4, 15 10.1038/nchem.1193
15. Ayme, J.-F.; Beves, J. E.; Leigh, D. A.; McBurney, R. T.; Rissanen, K.; Schultz, D. J. Am. Chem. Soc. 2012, 134, 9488 10.1021/ja303355v
16. Leigh, D. A.; Pritchard, R. G.; Stephens, A. J. Nat. Chem. 2014, 6, 978 10.1038/nchem.2056
17. Rice, C. R. Coord. Chem. Rev. 2006, 250, 3190 10.1016/j.ccr.2006.05.017
18. Steed, J. W. Chem. Soc. Rev. 2009, 38, 506 10.1039/B810364J
19. Amouri, H.; Desmarets, C.; Moussa, J. Chem. Rev. 2012, 112, 2015 10.1021/cr200345v
20. Ballester, P. Chem. Soc. Rev. 2010, 39, 3810 10.1039/b926229f
21. Klein, R. A. Chem. Phys. Lett. 2006, 425, 128 10.1016/j.cplett.2006.04.109
22. Mercer, D. J.; Loeb, S. J. Chem. Soc. Rev. 2010, 39, 3612 10.1039/b926226c
23. Goetz, S.; Kruger, P. E. Dalton Trans. 2006, 1277 10.1039/b514580e
24. Cui, F.; Li, S.; Jia, C.; Mathieson, J. S.; Cronin, L.; Yang, X.-J.; Wu, B. Inorg. Chem. 2012, 51, 179 10.1021/ic201417y
25. Yoon, J.; Kim, S. K.; Singh, N. J.; Kim, K. S. Chem. Soc. Rev. 2006, 35, 355 10.1039/b513733k
26. Amendola, V.; Boiocchi, M.; Colasson, B.; Fabbrizzi, L.; Rodriguez Douton, M.-J.; Ugozzoli, F. Angew. Chem., Int. Ed. 2006, 45, 6920 10.1002/anie.200602598
27. Riddell, I. A.; Smulders, M. M. J.; Clegg, J. K.; Hristova, Y. R.; Breiner, B.; Thoburn, J. D.; Nitschke, J. R. Nat. Chem. 2012, 4, 751 10.1038/nchem.1407
28. Riddell, I. A.; Ronson, T. K.; Clegg, J. K.; Wood, C. S.; Bilbeisi, R. A.; Nitschke, J. R. J. Am. Chem. Soc. 2014, 136, 9491 10.1021/ja504748g
29. Lee, C. H.; Na, H. K.; Yoon, D. W.; Won, D. H.; Cho, W. S.; Lynch, V. M.; Shevchuk, S. V.; Sessler, J. L. J. Am. Chem. Soc. 2003, 125, 7301 10.1021/ja029175u
30. Chen, Q. Y.; Chen, C. F. Tetrahedron Lett. 2004, 45, 6493 10.1016/j.tetlet.2004.06.135
31. Chmielewski, M. J.; Charon, M.; Jurczak, J. Org. Lett. 2004, 6, 3501 10.1021/ol048661e
32. Kang, S. O.; VanderVelde, D.; Powell, D.; Bowman-James, K. J. Am. Chem. Soc. 2004, 126, 12272 10.1021/ja046078n
33. Ilioudis, C. A.; Tocher, D. A.; Steed, J. W. J. Am. Chem. Soc. 2004, 126, 12395 10.1021/ja047070g
34. Kwon, J. Y.; Jang, Y. J.; Kim, S. K.; Lee, K. H.; Kim, J. S.; Yoon, J. Y. J. Org. Chem. 2004, 69, 5155 10.1021/jo049281+
35. Maeda, H.; Kusunose, Y. Chem.-Eur. J. 2005, 11, 5661 10.1002/chem.200500627
36. Vega, I. E.; Gale, P. A.; Light, M. E.; Loeb, S. J. Chem. Commun. 2005, 4913 10.1039/b510506d
37. Fujimoto, C.; Kusunose, Y.; Maeda, H. J. Org. Chem. 2006, 71, 2389 10.1021/jo052511f
38. Nishiyabu, R.; Palacios, M. A.; Dehaen, W.; Anzenbacher, P. J. Am. Chem. Soc. 2006, 128, 11496 10.1021/ja0622150
39. Zielinski, T.; Kedziorek, M.; Jurczak, J. Chem.-Eur. J. 2008, 14, 838 10.1002/chem.200700592
40. Li, Y.; Flood, A. H. Angew. Chem., Int. Ed. 2008, 47, 2649 10.1002/anie.200704717
41. Yoon, D.-W.; Gross, D. E.; Lynch, V. M.; Sessler, J. L.; Hay, B. P.; Lee, C.-H. Angew. Chem., Int. Ed. 2008, 47, 5038 10.1002/anie.200801426
42. Berryman, O. B.; Sather, A. C.; Hay, B. P.; Meisner, J. S.; Johnson, D. W. J. Am. Chem. Soc. 2008, 130, 10895 10.1021/ja8035652
43. Li, Y.; Flood, A. H. J. Am. Chem. Soc. 2008, 130, 12111 10.1021/ja803341y
44. Hua, Y.; Flood, A. H. Chem. Soc. Rev. 2010, 39, 1262 10.1039/b818033b
45. Sessler, J. L.; Cai, J.; Gong, H.-Y.; Yang, X.; Arambula, J. F.; Hay, B. P. J. Am. Chem. Soc. 2010, 132, 14058 10.1021/ja107098r
46. Lee, S.; Chen, C.-H.; Flood, A. H. Nat. Chem. 2013, 5, 704 10.1038/nchem.1668
47. Cai, J.; Sessler, J. L. Chem. Soc. Rev. 2014, 43, 6198 10.1039/C4CS00115J
48. Shi, G.; Gadhe, C. G.; Park, S.-W.; Kim, K. S.; Kang, J.; Seema, H.; Singh, N. J.; Cho, S. J. Org. Lett. 2014, 16, 334 10.1021/ol402819m
49. Use of high-purityNH4BF4 (e.g., 99.999% trace metal basis, Sigma-Aldrich, product no. 541893 Aldrich) and NH4PF6 (e.g., 99.99% trace metal basis, Sigma-Aldrich, product no. 216593 Aldrich) is necessary to obtain a chloride-free product. Attempts with salts of lower guaranteed purity failed to remove the last traces of chloride ion from samples of the knot.
50. Salt metathesis of [2·Cl](PF6)9 with NH4PF6 does not exchange all of the Cl- ions, even after exhaustive washings. It is necessary to first exchange all of the counterions of [2·Cl](PF6)9 for BF4- (with NH4BF4), forming [2](BF4)10, and then exchange the BF4- counterions for PF6- (with NH4PF6). This may be because the centrally bound Cl- is less strongly held in an intermediate [2·Cl](BF4)9 complex.
51. Danil de Namor, A. F.; Shehab, M. J. Phys. Chem. B 2003, 107, 6462 10.1021/jp0226174
52. The central cavities of the "empty" all-PF6- complexes of 1-3 are solvent and anion accessible (well-ordered PF6- anions are bound in the cavities of [1] and [3] in the X-ray crystal structures4,7).
53. H6 is in the shielding region of a pyridine ring (see Figure 2) and so is sensitive to minor structural changes in the circular helicates that occur upon binding.
54. The slow kinetics of exchange of all of the halides (Figure 3), even relatively weakly bound I-, in complexes of the pentafoil knot, [2·X] (PF6)9, suggests that the kinetic barrier to exchange may be due to slow release of a PF6- anion from [2](PF6)10 (a putative intermediate in the exchange process). The corresponding Solomon link and Star of David catenane complexes are all in fast exchange.
55. In some solvents the halide-PF6- anion-exchange experiments significantly changed the solubility of the knot/link complexes. Acetonitrile proved to be a good solvent for comparing the binding constants across the range of different sizes of knots and links with each halide ion.
56. The addition of Bu4NCl or Bu4NBr to [3](PF6)12 also produced ions corresponding to more than one halide-for-PF6- substitution.
57. The bipyridyl CH protons on the outside of the circular helicates (H4 and H5) are also electron-poor as a result of metal coordination to the bipyridyl groups, and can also interact with anions. From the 1H NMR spectra and by competition with calix[4]bipyrrole, these association constants are of the order ∼ 103 M-1 (I-), ∼103 M-1 (Br-), and ∼104 M-1 (CI-), typically several orders of magnitude less than halide binding associated with the central cavity of the knot or links.
58. Sessler, J. L.; An, D.; Cho, W. S.; Lynch, V.; Marquez, M. Chem. Commun. 2005, 540 10.1039/b412737d
59. The value of 450 equiv is a revision of the 90 equiv of AgPF6 stated to completely remove Cl- from [2·Cl](PF6)9 in MeCN in ref 5. The amount of AgPF6 required to remove Cl- from the pentafoil knot is reduced when using older bottles of the reagent. We speculate that this may be due to the presence of traces of fluoride arising from the decomposition of PF6-.
60. Luehrs, D. C.; Iwamoto, R. T.; Kleinberg, J. Inorg. Chem. 1966, 5, 201 10.1021/ic50036a009
61. Schmidtchen, F. P.; Berger, M. Chem. Rev. 1997, 97, 1609 10.1021/cr9603845
62. Edwards, S. J.; Valkenier, H.; Busschaert, N.; Gale, P. A.; Davis, A. P. Angew. Chem., Int. Ed. 2015, 54, 4592 10.1002/anie.201411805
63. Meluzzi, D.; Smith, D. E.; Arya, G. Annu. Rev. Biophys. 2010, 39, 349 10.1146/annurev.biophys.093008.131412
64. Farrell, J. D.; Lines, C.; Shepherd, J. J.; Chakrabarti, D.; Miller, M. A.; Wales, D. J. Soft Matter 2013, 9, 5407 10.1039/c3sm50711d
65. Jampani, V. S. R.; Skarabot, M.; Ravnik, M.; Copar, S.; Zumer, S.; Musevic, I. Phys. Rev. E 2011, 84, 031703 10.1103/PhysRevE.84.031703
66. Goldstein, R. E.; Moffatt, H. K.; Pesci, A. I.; Ricca, R. L. Proc. Natl. Acad. Sci. U.S.A. 2010, 107, 21979 10.1073/pnas.1015997107