Switching around two axles: Controlling the configuration and conformation of a hydrazone-based switch

Organic Letters

Volumn 13, Issue 1, 2011, Pages 30-33

  Su, Xin ^a   Aprahamian, Ivan ^a  

^a Dartmouth College   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 78650852909     PISSN: 15237060     EISSN: 15237052     Source Type: Journal    
DOI: 10.1021/ol102422h     Document Type: Article

References (68)

1. Sauvage, J.-P., Ed. Molecular Machines and Motors, Springer, New York: 2001.
2. Feringa, B. L., Ed. Molecular Switches; Wiley-VCH: Weinheim, Germany, 2001.
3. Kay, E. R.; Leigh, D. A.; Zerbetto, F. Angew. Chem., Int. Ed. 2007, 46, 72-191
4. Balzani, V.; Credi, A.; Venturi, M. Molecular Decices and Machines-Concepts and Perspectives for the Nanoworld; Wiley-VCH: Weinheim, Germany, 2008.
5. Michl, J.; Sykes, E. C. H. ACS Nano 2009, 3, 1042-1048
6. Stoddart, J. F. Chem. Soc. Rev. 2009, 38, 1802-1820
7. Collier, C. P.; Mattersteig, G.; Wong, E. W.; Luo, Y.; Beverly, K.; Sampaio, J.; Raymo, F. M.; Stoddart, J. F.; Heath, J. R. Science 2000, 289, 1172-1175
8. Flood, A. H.; Stoddart, J. F.; Steuerman, D. W.; Heath, J. R. Science 2004, 306, 2055-2056
9. Leigh, D. A.; Morales, M. A. F.; Pérez, E. M.; Wong, J. K. Y.; Saiz, C. G.; Slawin, A. M. Z.; Carmichael, A. J.; Haddleton, D. M.; Brouwer, A. M.; Buma, W. J.; Wurpel, G. W. H.; León, S.; Zerbetto, F. Angew. Chem., Int. Ed. 2005, 44, 3062-3067
10. Hess, H. Science 2006, 312, 860-861
11. Green, J. E.; Choi, J. W.; Boukai, A.; Bunimovich, Y.; Johnston-Halperin, E.; DeIonno, E.; Luo, Y.; Sheriff, B. A.; Xu, K.; Shin, Y. S.; Tseng, H.-R.; Stoddart, J. F.; Heath, J. R. Nature 2007, 445, 414-417
12. Browne, W. R.; Feringa, B. L. Annu. Rev. Phys. Chem. 2009, 60, 407-428
13. Omabegho, T.; Sha, R.; Seeman, N. C. Science 2009, 324, 67-71
14. Badjić, J. D.; Balzani, V.; Credi, A.; Silvi, S.; Stoddart, J. F. Science 2004, 303, 1845-1849
15. Berná, J.; Leigh, D. A.; Lubomska, M.; Mendoza, S. M.; Pérez, E. M.; Rudolf, P.; Teobaldi, G.; Zerbetto, F. Nat. Mater. 2005, 4, 704-710
16. Bonnet, S.; Collin, J. P.; Koizumi, M.; Mobian, P.; Sauvage, J.-P. Adv. Mater. 2006, 18, 1239-1250
17. Leblond, J.; Gao, H.; Petitjean, A.; Leroux, J.-C. J. Am. Chem. Soc. 2010, 132, 8544-8545
18. Wang, W.; Kaifer, A. E. Angew. Chem., Int. Ed. 2006, 45, 7042-7046
19. Nijhuis, C. A.; Ravoo, B. J.; Huskens, J.; Reinhoudt, D. N. Coord. Chem. Rev. 2007, 251, 1761-1780
20. Juluri, B. K.; Kumar, A. S.; Liu, Y.; Ye, T.; Yang, Y.-W.; Flood, A. H.; Fang, L.; Stoddart, J. F.; Weiss, P. S.; Huang, T. J. ACS Nano 2009, 3, 291-300
21. Parimal, K.; Witlicki, E. H.; Flood, A. H. Angew. Chem., Int. Ed. 2010, 49, 4628-4632
22. Balzani, V.; Credi, A.; Venturi, M. Pure Appl. Chem. 2003, 75, 541-547
23. Kottas, G. S.; Clarke, L. I.; Horinek, D.; Michl, J. Chem. Rev. 2005, 105, 1281-1376
24. Eelkema, R.; Pollard, M. M.; Vicario, J.; Katsonis, N.; Ramon, B. S.; Bastiaansen, C. W. M.; Broer, D. J.; Feringa, B. L. Nature 2006, 440, 163
25. Muraoka, T.; Kinbara, K.; Aida, T. Nature 2006, 440, 512-515
26. Russew, M.-M.; Hecht, S. Adv. Mater. 2010, 22, 3348-3360
27. Schilwa, M., Ed. Molecular Motors; Wiley-VCH: Weinheim, Germany, 2003.
28. Kelly, T. R.; de Silva, H.; Silva, R. A. Nature 1999, 401, 150-152
29. Leigh, D. A.; Wong, J. K. Y.; Dehez, F.; Zerbetto, F. Nature 2003, 424, 174-179
30. Hernández, J. V.; Kay, E. R.; Leigh, D. A. Science 2004, 306, 1532-1537
31. Fletcher, S. P.; Dumur, F.; Pollard, M. M.; Feringa, B. L. Science 2005, 310, 80-82
32. Dahl, B. J.; Branchaud, B. P. Org. Lett. 2006, 8, 5841-5844
33. Feringa, B. L. J. Org. Chem. 2007, 72, 6635-6652
34. Kelly, T. R.; Cai, X.; Damkaci, F.; Panicker, S. B.; Tu, B.; Bushell, S. M.; Cornella, I.; Piggott, M. J.; Salives, R.; Cavero, M.; Zhao, Y.; Jasmin, S. J. Am. Chem. Soc. 2007, 129, 376-386
35. -1). These differences in isomerization rates can be very important in future applications.
36. Qu, D.-H.; Feringa, B. L. Angew. Chem., Int. Ed. 2010, 49, 1107-1110
37. Whitesides, G. M.; Ismagilov, R. F. Science 1999, 284, 89-92
38. Stoddart, J. F. Nat. Chem. 2009, 1, 14-15
39. Landge, S. M.; Aprahamian, I. J. Am. Chem. Soc. 2009, 131, 18269-18271
40. In the crystal structure of QPH- E, the dihedral angle between the pyridyl ring and the quinolinyl ring is 10.453(48)°, and the torsion angles of N-N=C-C (pyridyl) and C=N-N-C (quinolinyl) are 2.516(279)° and -175.253(161)°, respectively.
41. Vickery, B.; Willey, G. R.; Drew, M. G. B. J. Chem. Soc., Perkin Trans. 2 1981, 1454-1458
42. Drew, M. G. B.; Vickery, B.; Willey, G. R. Acta Crystallogr., Sect. B: Struct. Sci. 1982, 38, 1530-1535
43. Frohberg, P.; Drutkowski, G.; Wagner, C. Eur. J. Org. Chem. 2002, 1654-1663
44. This ratio is less than what was observed (97:3) for our previously reported naphthyl-based system (see ref 12). This observation might arise from the additional H-bond between the N-H proton and the quinolinyl nitrogen, which can stabilize the Z configuration.
45. The naphthyl-based system (ref 12) showed that the Z / E isomerization rate is dependent on solvent polarity. This is an indication that the isomerization goes through the rotation mechanism and not the lateral shift one
46. Tobin, J. C.; Hegarty, A. F.; Scott, F. L. J. Chem. Soc. B 1971, 2198-2202
47. Wong, J. L.; Zady, M. F. J. Org. Chem. 1975, 40, 2512-2516
48. Pichon, R.; Le Saint, J.; Courtot, P. Tetrahedron 1981, 37, 1517-1524
49. The chemical shift of the N-H proton is influenced by the ring current effects of the naphthyl moiety, in addition to resonance assisted hydrogen-bonding (RAHB). For RAHB, please see
50. Bertolasi, V.; Gilli, P.; Ferretti, V.; Gilli, G. J. Am. Chem. Soc. 1991, 113, 4917-4925
51. Bertolasi, V.; Gilli, P.; Ferretti, V.; Gilli, G.; Vaughan, K. New J. Chem. 1999, 23, 1261-1267
52. Šimůnek, P.; Svobodová, M.; Bertolasi, V.; Pretto, L.; Lyčka, A.; Macháček, V. New J. Chem. 2007, 31, 429-438
53. These effects impede the direct comparison between the N-H chemical shifts of the different QPH isomers. Moreover, they complicate the analysis of the effect that the extra H-bond with the quinolinyl moiety has on the N-H proton, making the direct comparison with the previously published naphthyl-based system (ref 12), very difficult.
54. + isomerization process is too fast to be monitored by NMR spectroscopy, see ref 12.
55. Pretsch, E., Ed. Tables of Spectral Data for Structure Determination of Organic Compounds; Springer-Verlag: Berlin, Germany, 1989; Vol. 2.
56. The chemical shift of the equivalent proton to H8 in the starting material (ethyl-2-pyridylacetate) is 8.49 ppm. This clearly shows that proton H8 in QPH- E is influenced by both RAHB (see ref 17) and the ring current effect of the quinolinyl moiety. The chemical shift of proton H8 in QPH- Z (8.60 ppm) lends further support to this conclusion.
57. + shows that the pyridyl nitrogen proton is directed towards the quinolinyl group. This difference in orientation might stem from crystal packing considerations.
58. +, the dihedral angle between the pyridyl ring and the quinolinyl ring is 2.273(59)°, and the torsion angles of N-N=C-C (pyridyl) and C=N-N-C (quinolinyl) are 179.380(185)° and - 178.483(200)°, respectively.
59. Barbieri, G.; Benassi, R.; Lazzeretti, P.; Schenetti, L.; Taddei, F. Org. Magn. Resonance 1975, 7, 451-454
60. Mitchell, A. D.; Nonhebel, D. C. Tetrahedron Lett. 1975, 3859-3862
61. These systems usually adopt a planar structure that increases their π -delocalization, which in turn leads to resonance-assisted hydrogen bonding (ref 17). This behavior, the possibility of forming a six-membered H-bonded ring, in addition to the acquired NMR and UV-vis data, make us conclude that QPH- Z -H 2 2+ has a locked planar conformation as depicted in the figures.
62. Hosmane, R. S.; Liebman, J. F. Struct. Chem. 2009, 20, 693-697
63. The isomerization rate can be enhanced by either heating the sample, or as unpublished preliminary results indicate, by the addition of excess base to the solution that seems to catalyze the Z / E isomerization.
64. 3CN are 12.65 and 2.6, respectively: Eckert, F.; Leito, I.; Kaljurand, I.; Kütt, A.; Klamt, A.; Diedenhofen, M. J. Comput. Chem. 2009, 30, 799-810
65. We are showing the data with TFA to be consistent with the NMR spectroscopy data, which afforded sharper spectra with TFA than triflic acid.
66. The first protonation process has isosbestic points at λ = 268, 338, and 405 nm, and the second protonation process has isosbestic points at λ = 284, 213, and 391 nm.
67. de Silva, A. P.; Uchiyama, S. Nat. Nanotechnol. 2007, 2, 399-410
68. Pischel, U. Aust. J. Chem. 2010, 63, 148-164