Dipolar and Nonpolar Altitudinal Molecular Rotors Mounted on an Au(111) Surface

Journal of the American Chemical Society

Volumn 126, Issue 14, 2004, Pages 4540-4542

  Zheng, Xiaolai ^a   Mulcahy, Mary E ^a   Horinek, Dominik ^a   Galeotti, Francesco ^a   Magnera, Thomas F ^a   Michl, Josef ^a  

^a UNIVERSITY OF COLORADO   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

GOLD;

ARTICLE; DIMERIZATION; ELECTRIC FIELD; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; ROOM TEMPERATURE; ROTATION; STEREOISOMERISM; SYNTHESIS;

EID: 1842738608     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja039482f     Document Type: Article

References (55)

1. Tailored crystals are now being designed: Godinez, C. E.; Zepeda, G.; Garcia-Garibay, M. A. J. Am. Chem. Soc. 2002, 124, 4701.
2. Vacek, J.; Michl, J. New J. Chem. 1997, 21, 1259.
3. Gimzewski, J. K.; Joachim, C.; Schlitter, R. R.; Langlais, V.; Tang, H.; Johannsen, I. Science 1998, 281, 531.
4. Hersam, M. C.; Guisinger, N. P.; Lyding, J. W. Nanotechnology 2000, 11, 70.
5. Yasuda, R.; Noji, H.; Kinosita, K., Jr.: Yoshida. M. Cell 1998, 93, 1117. Yasuda, R.; Noji, H.; Kinosita, K., Jr.; Itoh, H. Nature 2001, 410, 898.
6. Yasuda, R.; Noji, H.; Kinosita, K., Jr.: Yoshida. M. Cell 1998, 93, 1117. Yasuda, R.; Noji, H.; Kinosita, K., Jr.; Itoh, H. Nature 2001, 410, 898.
7. Vacek, J.; Michl, J. Proc. Natl. Acad. Sci. U.S.A. 2001, 98, 5481.
8. Clarke, L. I.; Horinek, D.; Kottas, G. S.; Varaska, N.; Magnera, T. F.; Hinderer. T. P.; Horansky, R. D.; Michl, J.; Price, J. C. Nanotechnology 2002, 13, 533.
9. Jian, H.; Tour, J. M. J. Org. Chem. 2003, 68, 5091.
10. Horinek, D.; Michl, J. J. Am. Chem. Soc. 2003, 125, 11900.
11. Kelly, T. R.; Tellitu, I.; Sestelo, J. P. Angew. Chem., Int. Ed. Engl. 1997, 36, 1866. Kelly, T. R.; Silva, R. A.; De Silva, H.; Jasmin. S.; Zhao, Y. J. Am. Chem. Soc. 2000, 122, 6935.
12. Kelly, T. R.; Tellitu, I.; Sestelo, J. P. Angew. Chem., Int. Ed. Engl. 1997, 36, 1866. Kelly, T. R.; Silva, R. A.; De Silva, H.; Jasmin. S.; Zhao, Y. J. Am. Chem. Soc. 2000, 122, 6935.
13. Koumura, N.; Zijlstra, R. W. J.; van Delden, R. A.; Harada, N.; Feringa, B. L. Nature 1999, 401, 152. Koumura, N. L.; Geertsema, E. M.; van Gelder, M. B.; Meetsma, A.; Feringa, B. L. J. Am. Chem. Soc. 2002, 124, 5037. Leigh, D. A. ; Wong, J. K. Y.; Dehez, F.; Zerbetto, F. Nature 2003, 424, 174.
14. Koumura, N.; Zijlstra, R. W. J.; van Delden, R. A.; Harada, N.; Feringa, B. L. Nature 1999, 401, 152. Koumura, N. L.; Geertsema, E. M.; van Gelder, M. B.; Meetsma, A.; Feringa, B. L. J. Am. Chem. Soc. 2002, 124, 5037. Leigh, D. A. ; Wong, J. K. Y.; Dehez, F.; Zerbetto, F. Nature 2003, 424, 174.
15. Koumura, N.; Zijlstra, R. W. J.; van Delden, R. A.; Harada, N.; Feringa, B. L. Nature 1999, 401, 152. Koumura, N. L.; Geertsema, E. M.; van Gelder, M. B.; Meetsma, A.; Feringa, B. L. J. Am. Chem. Soc. 2002, 124, 5037. Leigh, D. A. ; Wong, J. K. Y.; Dehez, F.; Zerbetto, F. Nature 2003, 424, 174.
16. Tinkertoy is a trademark of Playskool, Inc., Pawtucket, RI 02862. and designates a toy construction set of wooden sticks insertable into connectors.
17. Kaszynski, P.; Michl, J. J. Am. Chem. Soc. 1988, 110, 5225.
18. Michl, J.; Kaszynski, P.; Friedli, A. C.; Murthy, G. S.; Yang, H.-C.; Robinson, R. E.; McMurdie, N. D.; Kim, T. In Strain and Its Implications in Organic Chemistry; de Meijere. A., Blechert, S., Eds.; NATO ASI Series, Vol. 273: Kluwer Academic Publishers: Dordrecht, The Netherlands. 1989: p 463.
19. Kaszynski, P.; Friedli, A. C.; Michl. J. J. Am. Chem. Soc. 1992, 114, 601.
20. Rausch, M. D.; Genetti. R. A. J. Org. Chem. 1970, 35, 3888.
21. Harrison, R. M.; Brotin, T.; Noll, B. C.; Michl, J. Organometallics 1997, 16, 3401.
22. Smith, J.; Jindřich, J.; Častulík, J.; Kottas, G.; Schwab. P.; Trujillo, M.; Rubio, S.; Brotin, T.; Michl, J., unpublished results.
23. Kabalka, G. W.; Namboodiri, V.; Wang, L. Chem. Commun. 2001, 775.
24. Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.
25. Brotin, T.; Pospíšil, L.; Fiedler. J.; King, B. T.; Michl, J. J. Phys. Chem. B 1998, 102, 10062.
26. Pospíšil, L.; Varaksa, N.; Magnera, T. F.; Brotin, T.; Noll, B. C.; Michl, J., unpublished.
27. BLYP, def-SV(P) basis set, with ECP-60-MWB for Hg, using the RI approximation: Eichkorn, K.; Weigend, F.; Treutler, O.; Ahlrichs, R. Chem. Phys. Lett. 1995, 242, 652, TURBOMOLE program suite, http://www.turbomole.de.
28. 13C spectra do not change down to -110 °C.
29. Almenningen, A.; Bastiansen, O.; Fernholt, L.; Cyvin, B. N.; Cyving, S. J.; Samdal, S. J. Mol. Struct. 1985, 128, 59.
30. -7 Torr for at least 2 h. The film was then heated to 450 °C for 30 min, allowed to cool under vacuum, and annealed with a hydrogen flame immediately before use. STM imaging showed large terraces of Au(111).
31. Rudolph Research AutoEL instrument.
32. -6 M solution onto a 5 MHz, 1" diameter, AT-cut quartz crystal with a polished gold surface.
33. A Physical Electronics model 5800 XPS spectrometer with a hemispherical analyzer, a resistive multichannel detector, and a monochromatic Al Kα line (1486.6 eV) X-ray source was used. Survey scans from 10 to 1000 eV were acquired with a pass energy of 187.5 eV in steps of 0.8 eV. Higher resolution spectra of Co, F, Hg, and S were obtained with a pass energy of 23.5 eV in steps of 0.1 eV and confirmed the presence of the elements expected for each sample. An attempt is underway to determine the abundance of bound and unbound thioether sulfur atoms, the degree of oxidation, and the likely role of Hg atoms in surface adhesion.
34. Imaged at room temperature with Nanoscope 3a. Digital Instruments, Inc., under hexadecane unless noted otherwise.
35. 2 based largely on the MOIL 6.2 code: Elber, R.; Roitberg, A.; Simmerling, C.; Goldstein, R.; Li, H.; Verkhiver, G.; Keasar, C.; Zhang, J.; Ulitsky, A. Comput. Phys. Commun. 1994, 91, 159, uses the UFF energy function: Rappe, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard. W. A., III; Skiff, W. M. J. Am. Chem. Soc. 1992, 114, 10024. Interaction with the metal surface has been modeled by bonds to selected Au atoms, all of which are fixed, and adding image charges as in: Okuno, Y.; Yokoyama, T.; Yokoyama, S.; Kamikado, T.; Mashiko, S. J. Am. Chem. Soc. 2002, 124, 7218. Electronic friction due to the motion of the image charges within the metal (Tomassone, M. S.; Widom, A. Phys. Rev. B 1997, 56, 4938) has been treated by Langevin dynamics (van Gunsteren, W. F.; Berendsen. H. J. C. Mol. Phys. 1982, 45, 637), with an integrator based on: Paterlini, M. G.; Ferguson, D. M. Chem. Phys. 1998, 236, 243.
36. 2 based largely on the MOIL 6.2 code: Elber, R.; Roitberg, A.; Simmerling, C.; Goldstein, R.; Li, H.; Verkhiver, G.; Keasar, C.; Zhang, J.; Ulitsky, A. Comput. Phys. Commun. 1994, 91, 159, uses the UFF energy function: Rappe, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard. W. A., III; Skiff, W. M. J. Am. Chem. Soc. 1992, 114, 10024. Interaction with the metal surface has been modeled by bonds to selected Au atoms, all of which are fixed, and adding image charges as in: Okuno, Y.; Yokoyama, T.; Yokoyama, S.; Kamikado, T.; Mashiko, S. J. Am. Chem. Soc. 2002, 124, 7218. Electronic friction due to the motion of the image charges within the metal (Tomassone, M. S.; Widom, A. Phys. Rev. B 1997, 56, 4938) has been treated by Langevin dynamics (van Gunsteren, W. F.; Berendsen. H. J. C. Mol. Phys. 1982, 45, 637), with an integrator based on: Paterlini, M. G.; Ferguson, D. M. Chem. Phys. 1998, 236, 243.
37. 2 based largely on the MOIL 6.2 code: Elber, R.; Roitberg, A.; Simmerling, C.; Goldstein, R.; Li, H.; Verkhiver, G.; Keasar, C.; Zhang, J.; Ulitsky, A. Comput. Phys. Commun. 1994, 91, 159, uses the UFF energy function: Rappe, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard. W. A., III; Skiff, W. M. J. Am. Chem. Soc. 1992, 114, 10024. Interaction with the metal surface has been modeled by bonds to selected Au atoms, all of which are fixed, and adding image charges as in: Okuno, Y.; Yokoyama, T.; Yokoyama, S.; Kamikado, T.; Mashiko, S. J. Am. Chem. Soc. 2002, 124, 7218. Electronic friction due to the motion of the image charges within the metal (Tomassone, M. S.; Widom, A. Phys. Rev. B 1997, 56, 4938) has been treated by Langevin dynamics (van Gunsteren, W. F.; Berendsen. H. J. C. Mol. Phys. 1982, 45, 637), with an integrator based on: Paterlini, M. G.; Ferguson, D. M. Chem. Phys. 1998, 236, 243.
38. 2 based largely on the MOIL 6.2 code: Elber, R.; Roitberg, A.; Simmerling, C.; Goldstein, R.; Li, H.; Verkhiver, G.; Keasar, C.; Zhang, J.; Ulitsky, A. Comput. Phys. Commun. 1994, 91, 159, uses the UFF energy function: Rappe, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard. W. A., III; Skiff, W. M. J. Am. Chem. Soc. 1992, 114, 10024. Interaction with the metal surface has been modeled by bonds to selected Au atoms, all of which are fixed, and adding image charges as in: Okuno, Y.; Yokoyama, T.; Yokoyama, S.; Kamikado, T.; Mashiko, S. J. Am. Chem. Soc. 2002, 124, 7218. Electronic friction due to the motion of the image charges within the metal (Tomassone, M. S.; Widom, A. Phys. Rev. B 1997, 56, 4938) has been treated by Langevin dynamics (van Gunsteren, W. F.; Berendsen. H. J. C. Mol. Phys. 1982, 45, 637), with an integrator based on: Paterlini, M. G.; Ferguson, D. M. Chem. Phys. 1998, 236, 243.
39. 2 based largely on the MOIL 6.2 code: Elber, R.; Roitberg, A.; Simmerling, C.; Goldstein, R.; Li, H.; Verkhiver, G.; Keasar, C.; Zhang, J.; Ulitsky, A. Comput. Phys. Commun. 1994, 91, 159, uses the UFF energy function: Rappe, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard. W. A., III; Skiff, W. M. J. Am. Chem. Soc. 1992, 114, 10024. Interaction with the metal surface has been modeled by bonds to selected Au atoms, all of which are fixed, and adding image charges as in: Okuno, Y.; Yokoyama, T.; Yokoyama, S.; Kamikado, T.; Mashiko, S. J. Am. Chem. Soc. 2002, 124, 7218. Electronic friction due to the motion of the image charges within the metal (Tomassone, M. S.; Widom, A. Phys. Rev. B 1997, 56, 4938) has been treated by Langevin dynamics (van Gunsteren, W. F.; Berendsen. H. J. C. Mol. Phys. 1982, 45, 637), with an integrator based on: Paterlini, M. G.; Ferguson, D. M. Chem. Phys. 1998, 236, 243.
40. 2 based largely on the MOIL 6.2 code: Elber, R.; Roitberg, A.; Simmerling, C.; Goldstein, R.; Li, H.; Verkhiver, G.; Keasar, C.; Zhang, J.; Ulitsky, A. Comput. Phys. Commun. 1994, 91, 159, uses the UFF energy function: Rappe, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard. W. A., III; Skiff, W. M. J. Am. Chem. Soc. 1992, 114, 10024. Interaction with the metal surface has been modeled by bonds to selected Au atoms, all of which are fixed, and adding image charges as in: Okuno, Y.; Yokoyama, T.; Yokoyama, S.; Kamikado, T.; Mashiko, S. J. Am. Chem. Soc. 2002, 124, 7218. Electronic friction due to the motion of the image charges within the metal (Tomassone, M. S.; Widom, A. Phys. Rev. B 1997, 56, 4938) has been treated by Langevin dynamics (van Gunsteren, W. F.; Berendsen. H. J. C. Mol. Phys. 1982, 45, 637), with an integrator based on: Paterlini, M. G.; Ferguson, D. M. Chem. Phys. 1998, 236, 243.
41. Varaksa, N.; Pospíšil, L.; Magnera, T. F.; Michl, J. Proc. Natl. Acad. Sci. U.S.A. 2002, 99, 5012.
42. Harrick, N. Internal Reflection Spectroscopy; John Wiley & Sons: New York, 1967. Mulcahy, M.; Berets, S.; Milosevic, M.; Michl, J. J. Phys. Chem. B 2004, 108, 1519.
43. Harrick, N. Internal Reflection Spectroscopy; John Wiley & Sons: New York, 1967. Mulcahy, M.; Berets, S.; Milosevic, M.; Michl, J. J. Phys. Chem. B 2004, 108, 1519.
44. Glass microscope slides with 20 nm of Ti and 200 nm of Au, deposited by thermal evaporation.
45. Pearce, H. A.; Sheppard, N. Surf. Sci. 1976, 59, 205.
46. Au(b)].
47. calcd/deg: 1273, 49, 24; 1150, 48, 43: 1091, 44, 71; 1072, 66, 60; 1047, 51, 82).
48. Michl, J.; Thulstrup, E. W. Spectroscopy with Polarized Light. Solute Alignment by Photoselection, in Liquid Crystals, Polymers, and Membranes; VCH Publishers: Deerfield Beach, FL, 1995.
49. Akiyama, R.; Matsumoto, T.; Kawai. T. Phys. Rev. B 2000, 62, 2034.
50. Sakai, A. In Advances in Materials Reasearch: Advances in Scanning Probe Microscopy; Sakurai, T., Watanabe, Y., Eds.; Springer-Verlag: New York, 2000; p 143. Hasegawa, Y.; Jia, J. F.; Sakurai, T.; Li, Z. Q.; Ohno. K.; Kawazoe, Y. In Advances in Materials Reasearch: Advances in Scanning Probe Microscopy; Sakurai. T., Watanabe. Y., Eds.; Springer-Verlag: New York, 2000; p 167.
51. Sakai, A. In Advances in Materials Reasearch: Advances in Scanning Probe Microscopy; Sakurai, T., Watanabe, Y., Eds.; Springer-Verlag: New York, 2000; p 143. Hasegawa, Y.; Jia, J. F.; Sakurai, T.; Li, Z. Q.; Ohno. K.; Kawazoe, Y. In Advances in Materials Reasearch: Advances in Scanning Probe Microscopy; Sakurai. T., Watanabe. Y., Eds.; Springer-Verlag: New York, 2000; p 167.
52. Differential BHI at 5 kHz 0.2 Å vertical modulation of the tip position with lock-in detection and interleaved scanning with alternating polarity.
53. At room temperature, thioether sulfur atoms are likely to move from one to another Au atom with fair frequency. Even the much more strongly attached thiols diffuse readily on the Au surface: Barrena, E.; Ocal, C.; Salmeron, M. J. Chem. Phys. 1999, 111. 9797.
54. For calculated induction of unidirectional rotation of a segment of a chiral molecule by a linearly polarized laser pulse, see: Hoki. K.; Yamaki, M.; Koseki. S.; Fujimura, Y. J. Chem. Phys. 2003, 118, 497; 2003, 119, 12393. In our case, chirality is present but is not required.
55. For calculated induction of unidirectional rotation of a segment of a chiral molecule by a linearly polarized laser pulse, see: Hoki. K.; Yamaki, M.; Koseki. S.; Fujimura, Y. J. Chem. Phys. 2003, 118, 497; 2003, 119, 12393. In our case, chirality is present but is not required.