Multiple electron tunneling paths across self-assembled monolayers of alkanethiols with attached ruthenium(II/III) redox centers

Journal of Physical Chemistry

Volumn 100, Issue 48, 1996, Pages 18852-18858

  Finklea, Harry O ^a   Liu, Luna ^a   Ravenscroft, Melissa S ^a   Punturi, Sesto ^a  

^a WEST VIRGINIA UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33751061530     PISSN: 00223654     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp962831q     Document Type: Article

References (56)

1. Chidsey, C. E. D. Science 1991, 257, 919-22.
2. Evidence supporting this assumption has been reported.3-4
3. Becka, A. M.; Miller, C. J. J. Pli\s. Cliem. 1992. 96, 2657-68.
4. Xu, J.; Li, H.-L.; Zhang, Y. J. Phys. Cliem. 1993. 97, 11497-500.
5. Dubois, L. H.; Nuzzo."R. G. Anmi. Ret: Phys. Cliem. 1992, 43. 437-63.
6. Smalley, J. F.; Feldberg, S. W.; Chidsey, C. E. D.; Linford, M. R.; Newton, M. R.; Liu, Y.-P. J. Phys. Chein. 1995, 99, 13141-9.
7. Weber, K.; Creager, S. E. Anal. Cliem. 1994, 66. 3164-72.
8. Hocken, L. A.; Creager, S. E. Langmiiir 1995, //, 2318-21.
9. Weber, K.; Hockett, L A.; Steiger, S.; Creager, S. E. Presented at the 188th Electrochemical Society Meeting, ChicagoIlL, Oct. 8-13. 1995, No. 1024.
10. Tender, L.; Carter, M. T.; Murray, R. W. Anal. Cliem. 1994, 66, 3173-81.
11. Richardson, J. N.; Peck, S. R.; Curtin, L. S.; Tender, L. M.; Terrill. R. H.; Carter, M. T.; Murray, R. W.; Rowe, G. K.; Creaaer, S. E. J. Plm. Chem. 1995, 99, 766-72.
12. Rowe, G. K.; Carter, M. T.: Richardson, J. N.: Murray, R. W. Langmuir 1995. 11, 1797-806.
13. Richardson, J. N.; Rowe, G. K.; Carter, M. T.; Tender, L. M.; Curtin. L. S.; Peck. S. R.; Murray, R. W. Eleclrochim. Ada 1995,40, 1331 8.
14. Carter, M. T.: Rowe, G. K.; Richardson, J. N.; Tender, L. M.; Terrill. R. H.; Murray, R. W. J. Am. Chem. Sot: 1995, 117, 2896-9.
15. Finklea, H. O.; Hanshew, D. D. J. Am. Chem. Soc. 1992, 114, 3173-81.
16. Finklea, H. O.; Ravenscroft, M. S.; Snider, D. A. Langninir 1993, 9, 223-7.
17. Ravenscroft, M. S.; Finklea, H. O. J. Pli\s. Cliem. 1994, 98, 384350.
18. Sons, S.; Clark. R. A.; Bowden, E. F.; Tarlov, M. J. J. P/ivs. Client. 1993, 97, 6564-72.
19. Bowden, E. F. Presented at the 188th Electrochemical Society Meeting, Chicago, IL, Oct. 8-13, 1995; No. 857.
20. Terrettaz, S.; Becka, A. M.; Traub, M. J.; Fettinser, J. C.; Miller, C. J. J. Phys. Chem. 1995, 99, 11216-24. " .
21. Liu, Y.-P.; Newton, M. D. J. Plm. Chem. 1994, 9S, 7162-9.
22. Finklea, H. O. Eleclroanal. Chem. 1996, 19, 109-335.
23. A similar value for βis found for electron hopping between gold clusters coated with alkanethiol SAMs.24
24. Terrill, R. H.; Postlethwaite, T. A.; Chen, C; Poon, C.-D.; Terzis, A.; Chen, A.; Hutchison, J. E.; Clark, M. R.; Wignall, G.; Londono, J. D.; Superfine, R.; Falvo, M.; Johnson, C. S.: Samulski, E. T.; Murray. R. W. J. Am. Chem. Soc. 1995, 117, 12537-48.
25. Liang, C.; Newton. M. D. J. Phys. Chem. 1993, 97, 3199-211.
26. (a) Li, T. T.-T.; Liu, H. Y.; Weaver, M. J. Am. Chem. Soc. 1984, 106, 1233-9.
27. (b) Li, T. T.-T.; Weaver, M. J. J. Am. Cliem. Sue. 1984. 106, 6107-8.
28. Forster, R. J.; Faulkner, L. R. J. Am. Chem. Soc. 1994, 116. 544452.
29. Finklea. H. O.; Hanshew, D. D. J. Electroanal. Cliem. 1993, 347, 327-340.
30. L. Liu, M. S. thesis, West Virginia University, 1994.
31. Fletcher, S.; Hörne, M. D. J. Electroanal. Chem. 1991, 279, 2979.
32. CV's for surface-bound redox centers are reversible at room temperature if the standard rate constant in s~' is more than 100 times larger than the scan rate in V/s.
33. Early efforts (crystallization, column Chromatograph)') to remove this impurity from the desired complex were not successful. More recently, we have succeeded in separating the impurity and product using column chromatosraphy on reverse-phase C|g silica with 0.2# NHjPFo, adjusted to pH 2.5 with CF3COOH.
34. Bain, C. D.; Whitesides, G. M. Lanynuir 1989, 5, 1370-1378.
35. Lee, T. R.; Carey, R. I.; Biebuyck, H. A.; Whitesides, G. M. Lam-muir 1994, 10, 741-9.
36. Creacer, S. E.; Clarke, J. Langmuir 1994, 10, 3675-83.
37. Smith, C. P.; White, S. Anal. Chem. 1992, 64, 2398-405.
38. Fawcett, W. R. J. Electroanal. Chem. 1994, 37S, 117-24.
39. Creaaer, S. E.; Rowe, G. K. Anal. Chim. Ada 1991, 246, 233-9.
40. Rowe, G. K.; Creaeer, S. E. J. Phys. Chem. 1994, 98, 5500-7.
41. Laviron, E. J. Electroanal. Chem.'1979, 101, 19-28.
42. Laviron, E. J. Electroanal. Chem. 1979, 97, 135-149.
43. Bowden has described a superior method for extracting rate constants from current transients which does not introduce as much noise and does not require an assumption about the transfer coefficient; see: Nahir, T. M.; Clark. R. A.; Bowden. E. F. Anal. Chem. 1994, 66, 2595-8.
44. A reviewer pointed out that solvent relaxation modes could be slower when the redox center is partially buried in the monolayer and suggested that this could contribute to the kinetic heterogeneity. However, solvent relaxation times are anticipated to be unimportant in rate expressions for strongly nonadiabatic electron transfer, such as is the case in this system; see ref 17.
45. For a single Tafel plot, visual fits of the theoretical Tafel lines to the data points have an uncertainty of ±0.1 eV. Because of scatter in the data points, the same uncertainty is obtained when a "least-squares" minimization algorithm is applied to achieve an optimum fit between data and theory.
46. A parity rule has been invoked to account for large changes in electronic coupling with the insertion of one bond in a multistrand link between an electron donor and acceptor: see: Shephard, M. J.; PaddonRow, M. N. J. Phys. Chem. 1995, 99, 17497-500. Whether the parity rule can be applied to a system consisting of many unlinked single strands remains to resolved.
47. Note that temperature is an explicit variable in just the Fermi distribution and the density of redox donor or acceptor states; see eq 1. In particular, the tunneling parameter βis assumed to be independent of temperature.
48. Beratan, D. N.: Onuchic, J. N.; Hopfield, J. J. J. Chem. Pins. 1987, 86, 4488-9S.
49. Gennet, T.; Weaver, M. J. Anal. Chem. 1984, 56, 1444-8.
50. Iwasita, T.; Schmickler, W.; Schultze. J. W. Der. Bimsenges. Pirn. Chem. 1985, 89, 138-142.
51. Wipf, D. O.; Kristensen, E. W.; Deakin, M. R.; Wiahtman, R. M. Anal. Chem. 1988, 60, 306-10.
52. Hoffmann, R. Ace. Chem. Res. 1971, 4, 1-9.
53. Jordan, K. D.; Paddon-Row, M. N. Client. Rei: 1992, 92, 395410.
54. Newton, M. D. Chem. Kei: 1991, 91, 767-92.
55. Onuchic, J. N.; Beratan, D. N. J. Chem. Pli\s. 1990, 92, 722-33.
56. de Rese, P. J. F.; Williams, S. A.; Therien, M. J. Science 1995, 269, 1409-13-4