Alkanethiolate gold cluster molecules with core diameters from 1.5 to 5.2 nm: Core and monolayer properties as a function of core size

Langmuir

Volumn 14, Issue 1, 1998, Pages 17-30

  Hostetler, Michael J ^a   Wingate, Julia E ^a   Zhong, Chuan Jian ^b   Harris, Jay E ^a   Vachet, Richard W ^a   Clark, Michael R ^a   Londono, J David ^c   Green, Stephen J ^a   Stokes, Jennifer J ^a   Wignall, George D ^c   Glish, Gary L ^a   Porter, Marc D ^b   Evans, Neal D ^d   Murray, Royce W ^a  

^a UNIVERSITY OF NORTH CAROLINA   (United States)

^b IOWA STATE UNIVERSITY   (United States)

^c OAK RIDGE NATIONAL LABORATORY   (United States)

^d OAK RIDGE INSTITUTE FOR SCIENCE AND EDUCATION   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

DIFFERENTIAL SCANNING CALORIMETRY; ELECTRONIC PROPERTIES; FOURIER TRANSFORM INFRARED SPECTROSCOPY; GOLD; MASS SPECTROMETRY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; ORGANIC COMPOUNDS; SYNTHESIS (CHEMICAL); THERMOGRAVIMETRIC ANALYSIS; TRANSMISSION ELECTRON MICROSCOPY; ULTRAVIOLET SPECTROSCOPY; X RAY PHOTOELECTRON SPECTROSCOPY;

CONTACT ANGLE MEASUREMENT; DODECANETHIOLATE; SMALL ANGLE X RAY SCATTERING; THERMAL DESORPTION MASS SPECTROMETRY;

MONOLAYERS;

EID: 0032488526     PISSN: 07437463     EISSN: None     Source Type: Journal    
DOI: 10.1021/la970588w     Document Type: Article

References (119)

1. Matijević, E. Curr. Opin. Coll. Interface Sci. 1996, 1, 176-183.
2. (b) Belloni, J. Curr. Opin. Coll. Interface Sci. 1996, 1, 184-196.
3. (c) Klabunde, K. J.; Stark, J.; Koper, O.; Mohs, C.; Park, D. G.; Decker, S.; Jiang, Y.; Lagadic, L; Zhang, D. J. Phys. Chem. 1996, 700, 12142-12153.
4. (d) Haberland, H., Ed. Clusters of Atoms and Molecules; Springer-Verlag: New York, 1994.
5. (e) Clusters and Colloids. From Theory to Applications; Schmid, G., Ed.; VCH: New York, 1994.
6. (f) Heinglein, A. Ber. Bunsenges Phys. Chem. 1995, 99, 903-913.
7. (g) Schmid, G. Chem. Rev. 1992, 92, 1709-1727.
8. (h) Fendler, J. H.; Meldrum, F. C. Adv. Mater. 1995, 7, 607-632.
9. (i) Schmid, G.; Maihack, V.; Lantermann, F.; Peschel, S. J. Chem. Soc., Dalton Trans. 1996, 589-595.
10. (a) Schon, G.; Simon, U. Colloid Polym. Sci. 1995, 273, 101-117.
11. (b) Schon, G.; Simon, U. Colloid Polym. Sd. 1995, 273, 202-218.
12. (a) Weller, H. Angew. Chem., Int. Ed. Engl. 1993, 32, 41-53.
13. (b) Murray, C. B.; Kagan, C. R.; Bawendi, M. G. Science 1995, 270,1335-1338.
14. (c) Guzelian, A. A.; Katari, J. E. B.; Kadavanich, A. V.; Banin, U.; Hamad, K.; Juban, E.; Alivasatos, A. P.; Wolters, R. H.; Arnold, C. C.; Heath, J. R. J. Phys. Chem. 1996, 100, 7212-7219.
15. (d) Ahmadi, T. S.; Wang, Z.L.; Henglein, A.; El-Sayed, M. A. Chem. Mater. 1996, 8, 1161-1163.
16. (e) Ahmadi, T. S.; Wang, Z. L.; Green, T. C.; Henglein, A.; El-Sayed, M. A. Science 1996, 272, 1924-1926.
17. (f) Harfenist, S. A.; Wang, Z. L.; Alvarez, M. M.; Vezmar, I.; Whetten, R. L. J. Phys. Chem. 1996, 100, 13904-13910.
18. (a) Optical Properties of Metal Clusters; Kreibig, U.; Vollmer, M., Eds. Springer-Verlag: New York, 1995.
19. (b) Underwood, S.; Mulvaney, P. Langmuir 1994, 10, 3427-3430.
20. (c) Mulvaney, P. Langmuir 1996, 12, 788-800.
21. (d) Kreibig, U.; Fauth, K.; Quinten, M.; Schönauer, D. Z. Phys. D 1989, 12, 505.
22. (a) Brust, M.; Walker, M.; Bethell, D.; Schiffrin, D. J.; Whyman, R. J. Chem. Soc., Chem. Commun. 1994, 801-802.
23. (b) Brust, M.; Fink, J.; Bethell, D.; Schiffrin,D. J.;Kiely, C. J. J. Chem. Soc., Chem. Commun. 1995, 1655-1656.
24. (c) Brust, M.; Bethell, D.; Schiffrin, D. J.; Kiely, C. J. Adv. Mater. 1995, 7, 795-797.
25. (d) Bethell, D.; Brust, M.; Schiffrin, D. J.; Kiely, C. J. J. Electroanal. Chem. 1996, 409, 137-143.
26. (a) Terrill, R. H.; Postlethwaite, T. A.; Chen, C.-H.; Poon, C.-D.; Terzis, A.; Chen, A.; Hutehison, J. E.; Clark, M. R.; Wignall, G.; Londono, J. D.; Superfine, R.; Falvo, M.; Johnson, C. S., Jr.; Samulski, E. T.; Murray, R. W. J. Am. Chem. Soc. 1995, 117, 12537-12548.
27. (b) Hostetler, M. J.; Green, S. J.; Stokes, J. J; Murray, R. W. J. Am. Chem. Soc. 1996, 118, 4212-4213.
28. (c) Hostetler, M. J.; Stokes, J. J.; Murray, R. W. Langmuir 1996, 12, 3604-3612.
29. (d) Green, S. J.; Stokes, J. J.; Hostetler, M. J.; Pietron, J. J.; Murray, R. W. J. Phys. Chem. B 1997, 101, 2663.
30. (e) Hostetler, M. J.; Murray, R. W. Curr. Opin. Colloid Interface Sci. 1997, 2, 42-50.
31. (f) Ingram, R. S.; Hostetler, M. J.; Murray, R. W. J. Am. Chem. Soc. 1997, 119, 9175.
32. (g) Ingram, R. S.; Hostetler, M. J.; Murray, R. W.; Schaaff, T. G.; Khoury, J. T.; Whetten, R. L.; Bigioni, T. P.; Guthrie, D. K.; First, P. N. J. Am. Chem. Soc. 1997, 119, 9279.
33. (h) Templeton, A. C.; Hostetler, M. J.; Kraft, C. T.; Murray, R. W., submitted for publication.
34. (a) Leff, D. V.; Ohara, P. C.; Heath, J. R.; Gelbart, W. M. J. Phys. Chem. 1995, 99, 7036-7041.
35. (b) Badia, A.; Gao, W.; Singh, S.; Demers, L.; Cuccia, L.; Reven, L. Langmuir 1996, 12, 1262-1269.
36. (c) Badia, A.; Singh, S.; Demers, L.; Cuccia, L.; Brown, G. R.; Lennox, R. B. Chem. Eur. J. 1996, 2, 359-363.
37. (d) Whetten, R. L.; Khoury, J. T.; Alvarez, M. M.; Murthy, S.; Vezmar, I; Wang, Z. L.; Stephens, P. W.; Cleveland, C. L.; Luedtke, W. D.; Landman, U. Adv. Mater. 1996, 8, 428-433.
38. (e) Ohara, P. C.; Leff, D. V.; Heath, J. R.; Gelbart, W. M. Phys. Rev. Lett. 1995, 75, 3466-3469.
39. (f) Luedtke, W. D.; Landman, U. J. Phys. Chem. 1996, 100, 13323-13329.
40. (g) Weisbecker, C. S.; Merritt, M. V.; Whitesides, G. M. Langmuir 1996, 12, 3763-3772.
41. (h) Leff, D. V.; Brandt, L.; Heath, J. R. Langmuir 1996, 12, 4723-4730.
42. (i) Alvarez, M. M.; Khoury, J. T.; Schaaff, T. G.; Shafigullin, M. N.; Vezmar, I; Whetten, R. L. J. Phys. Chem. B 1997, 101, 3706.
43. (j) Cleveland, C. L.; Landman, U.; Shafigullin, M.; Stephens, P. W.; Whetten, R. L. Z. Phys.D 1997, 40, 503.
44. (k) Vezmar, I.; Alvarez, M. M.; Khoury, J. T.; Salisbury, B. E.; Whetten, R. L. Z. Phys. D 1997, 40, 147.
45. (l) Johnson, S. R.; Evans, S. D.; Mahon, S. W.; Ulman, A. Langmuir 1997, 13, 51-57.
46. (m) Badia, A.; Cuccia, L.; Demers, L.; Morin, F.; Lennox, R. B. J. Am. Chem. Soc. 1997, 119, 2682-2692.
47. (n) Yonezawa, T.; Tominaga, T.; Richard, D. J. Chem. Soc., Dalton Trans. 1996, 783-789.
48. (o) Alvarez, M. M.; Khoury, J. T.; Schaaf, T. G.; Shafigullen, M.; Vezmar, I.; Whetten, R. L. Chem. Phys. Lett. 1997, 266, 91.
49. (p) Yonezawa, T.; Sutoh, M.; Kunitake, T. Chem. Lett. 1997, 619.
50. (q) Buining, P. A.; Humbel, B. M.; Philipse, A. P.; Verkleij, A. J. Langmuir 1997, 13, 3921.
51. (r) Whetten, R. L., personal communication.
52. (s) Andrews, R. P.; Bielefeld, J. D.; Henderson, J. I.; Janes, D. B.; Kolagunta, V. R.; Kubiak, C. P.; Mahoney, W. J.; Osifchin, R. G. Science 1996, 273, 1690-1693.
53. (t) Andrews, R. P.; Bein, T.; Dorogi, M.; Feng, S.; Henderson, J. I.; Kubiak, C. P.; Mahoney, W.; Osifchin, R. G.; Reifenberger, R. Science 1996, 272, 1323-1325.
54. Recent work in this lab indicates that the transition between metallic and molecular behavior occurs at a gold core size of ∼40 atoms; see ref 6g.
55. (a) Dubois, L. H.; Nuzzo, R. G. Annu. Rev. Phys. Chem. 1992, 43, 437-463.
56. (b) Ulman, A. An Introduction to Ultrathin Organic Films, Academic: New York, 1991.
57. (c) Bain, C. D.; Whitesides, G. M. Angew. Chem., Int. Ed. Engl. 1989, 28, 506-512.
58. (d) Ulman, A. Chem. Rev. 1996, 96, 1533-1554.
59. (a) Handbook of Preparative Inorganic Chemistry; Brauer, G., Ed.; Academic: New York, 1965, pp 1054-1059.
60. (b) Block, B. P. Inorg. Syn. 1953, 4, 14-17.
61. 4-mole ratios of 5:1 and 2:1) slightly increased average particle size (FWHM, 19 and 21 Hz, respectively). A mole ratio of 1:1 significantly increased particle size (FWHM = 32 Hz) with ∼50% toluene-insoluble product; a mole ratio of 1:2 gave only insoluble product.
62. Shirley, D. A. Phys. Rev. B 1972, 5, 4709-4714.
63. (a) Hendricks, R. W. J. Appl. Phys. 1978, 11, 15.
64. (b) Wignall, G. D.; Lin, J. S.; Spooner, S. J. Appl. Crystallogr. 1990, 23, 241-245.
65. (c) Russell, T. P.; Lin, J. S.; Spooner, S.; Wignall, G. D. J. Appl. Crystallogr. 1988, 21, 629-638.
66. (d) Guinier, A.; Fournet, G. Small Angle Scattering of X-rays; John Wiley: New York, 1955.
67. (e) Glatter, O.; Kratky, O., Eds. Small Angle X-ray Scattering; Academic: New York, 1982.
68. (f) Brill, O. L; Weil, C.G.; Schmidt, P. W. J. Coll. Interface Sci. 1968, 27, 479-492.
69. (g) Brill, O. L.; Schmidt, P. W. J. Appl. Phy. 1968, 39, 2274.
70. (h) Motte, L.; Billoudet, F.; Pileni, M. P. J. Phys. Chem. 1995, 99, 16425-16429.
71. (a) McNeille, A.; Brown, D. H.; Smith, W.E.; Gibson, M.; Watson, L J. Chem. Soc., Dalton Trans. 1980, 767-770.
72. (b) Puddephatt, R. J. In Comprehensive Coordination Chemistry, Wilkinson, G.; Gillard, R. D.; McCleverty, J. A., Eds.; Pergamon: New York, 1987; Vol. 5; pp 861-923.
73. Hayat, M. A., Ed. Colloidal Gold; Academic: New York, 1989; Vol. 1.
74. 5a
75. A sphere, covered by tightly packed alkanethiolate ligands can achieve a maximum coverage of 43%; thus, the presence effaces, edges, and corners significantly increases the ligand density of a polyhedron with the same average diameter.
76. Polydispersity of cluster sizes in a preparation will bias the calculated surface coverage; thus, these results only apply to a hypothetical average cluster size.
77. 2. Simple geometric considerations reveal that this calculation is equivalent to using 57% of the surface area of each edge Au atom and 83% of each corner Au atom. These contributions will clearly overestimate the actual surface area of the polyhedron; thus, coverages obtained from these calculations should be considered maximum values. Also latent in these assumptions is the approximation that the alkanethiolates will indiscriminately bind to the polyhedron to form a maximally packed surface.
78. Sellers, H.; Ulman, A.; Schnidman,Y.; Eilers, J. E. J. Am. Chem. Soc. 1993, 111, 9389-9401.
79. (a) Homans, S. W. A Dictionary of Concepts in NMR; Clarendon: Oxford, 1989.
80. 3 group).
81. We thank Professor Robert L. Whetten, Igor Vezmar, and T. Gregory Schaaff of the School of Physics at the Georgia Institute of Technology for the acquisition of this data.
82. 8 solution of the (0°,2X,sd) cluster preparation at 90°C, which leads (shown by NMR) to partial monolayer decomposition (<15%), forming di(dodecyl)disulfide and a cluster material that was still stable. Current studies demonstrate that alkyldisulfides cannot exchange onto clusters, so formation of dodecyldisulfide during (90°,2X,sd) cluster synthesis would not allow the full monolayer reconstitution even'after the reaction was returned to room temperature.
83. (a) Bain, C. D.; Biebuyck, H. A.; Whitesides, G. M. Langmuir 1989, 5, 723-727.
84. (b) Hüfner, S. Photoelectron Spectroscopy, 2nd Ed.; Springer-Verlag: New York, 1996.
85. (c) Porter, M. D., unpublished results.
86. van der Putten, D.; Zanoni, R.; Coluzza, C.; Schmid, G. J. Chem. Soc., Dalton Trans. 1996, 1721-1725.
87. 1H NMR spectroscopy, so it is highly unlikely that such species could contribute any XPS band intensity.
88. (b) Zubragel, Ch.; Deuper, C.; Scheider, F.; Neumann, M.; Grunze, M.; Schertel, A.; Woll, Ch. Chem. Phys. Letters 1995, 238, 308-312.
89. (c) Castner, D. G.; Hinds, K.; Grainger, D. W. Langmuir 1996, 12, 5083-5086.
90. Volokitin, Y.; Sinzig, J.; de Jongh, L. J.; Schmid, G.; Vargaftik, M. N.; Moiseev, I. I. Nature 1996, 384, 621-623.
91. (a) Kreibig, U.; Fauth, K.; Granquist, C.-G.; Schmid Z. Phys. Chem. 1990, 169, 11-28.
92. (b) Benfield, R. E.; Creighton, J. A.; Eadon, D. G.; Schmid, G. Z. Phys. D 1989, 12, 533-536.
93. (c) Kreibig, U.; Fauth, K.; Quinten, M.; Schönauer, D. Z. Phys. D 1989, 12, 505-514.
94. (d) Fauth, K.; Kreibig, U.; Schmid, G. Z. Phys. D 1989, 12, 515-520.
95. (e) Kreibig, U. Sol. State Commun. 1978, 28, 767-769.
96. (a) Grabar, K. C.; Freeman, R. G.; Hommer, M. B.; Natan, M. J. Anal. Chem. 1995, 67, 735-743.
97. (b) Freeman, R. G.; Grabar, K. C.; Allison, K. J.; Bright, R. M.; Davis, J. A.; Guthrie, A. P.; Hommer, M. B.; Jackson, M. A.; Smith, P. C.; Walter, D. G.; Natan, M. J. Science 1995, 267, 1629-1632.
98. (c) Chumanov, G.; Sokolov, K.; Gregory, B. W.; Cotton, T. M. J. Phys. Chem. 1995, 99, 9466-9471.
99. (a) Nuzzo, R. G.; Fusco, F. A.; Allara, D. L. J. Am. Chem. Soc. 1987, 109, 2358-2368.
100. (b) Nuzzo, R. G.; Dubois, L. H.; Allara, D. L. J. Am. Chem. Soc. 1990, 112, 558-569.
101. (c) Porter, M. D.; Bright, T. B.; Allara, D. L.; Chidsey, C. E. D. J. Am. Chem. Soc. 1987, 109, 3559-3568.
102. (a) Snyder, R. G; Strauss, H. L.; Elliger, C. A. J. Phys. Chem. 1982, 86, 5145-5150.
103. (b) Snyder, R. G.; Maroncelli, M.; Strauss, H. L.; Hallmark, V. M. J. Phys. Chem. 1986, 90, 5623-5630.
104. (a) Hayashi, M.; Shiro, Y.; Murata, H. Bull. Chem. Soc. Jpn. 1966, 39, 112-117.
105. (b) Bryant, M. A.; Pemberton, J. E. J. Am. Chem. Soc. 1991, 113, 8284-8293.
106. x] can be compared between each spectrum to obtain relative concentrations of near surface C-C gauche defects.
107. Ito, T. In High Pressure Science and Technology, Sixth AIRAPT Conference, Timmerhaus, K. D.; Barber, M. S., Eds.; Plenum: New York, 1977; Vol. 1, pp 482-490.
108. Both studies reported a DSC trace for a dodecanethiolate protected cluster whose average core size was approximately that of the 314 atom truncated octahedron.
109. (a) Badia, A.; Back, R.; Lennox, R. B. Angew. Chem. Int. Ed. Engl. 1994, 33, 2332-2335.
110. (b) Fenter, P.; Eisenberger, P.; Liang, K. S. Phys. Rev. Lett. 1993, 70, 2447-2450.
111. (a) Folkers, J. P.; Gorman, C. B.; Laibinis, P. E.; Buchholz, S.; Whitesides, G. M.; Nuzzo, R. G. Langmuir 1995, 11, 813-824, and references therein.
112. (b) Calistri-Yeh, M.; Kramer, E. J.; Sharma, R.; Zhao, W.; Rafailovich, M. H.; Sokolov, J.; Brock, J. D. Langmuir 1996, 12, 2747-2755.
113. (c) Woodward, J. T.; Ulman, A.; Schwartz, D. K. Langmuir 1996, 12, 3626-3629.
114. (a) Harris, J. E. M.A. Thesis, University of North Carolina, Chapel Hill, NC, 1996.
115. (b) Bain, C. D.; Troughton, E. B.; Tao, Y.-T.; Evall, J.; Whitesides, G. M.; Nuzzo, R. G. J. Am. Chem. Soc. 1989, 111, 321-335.
116. (a) Jaffey, D. M.; Madix, R. J. Surf. Sci. 1994, 311, 159-171.
117. (b) Nuzzo, R. G.; Zegarski, B. R.; Dubois, L. H. J. Am. Chem. Soc. 1987, 109, 733-740.
118. When the sample is inserted and the temperature immediately raised to 200°C, the total ion and disulfide ion currents are very broad peaks (30-40°C). This result may be due to physisorbed or weakly adsorbed disulfides. Holding the sample at 50°C for 4 min effectively eliminates this type of desorption feature. Further studies will examine this phenomenon.
119. 2S.