Thin-film molecular materials based on tetrametallic 'squares': Nanoscale porosity and size-selective guest transport characteristics

Journal of the American Chemical Society

Volumn 121, Issue 3, 1999, Pages 557-563

  Bélanger, Suzanne ^a   Hupp, Joseph T ^a   Stern, Charlotte L ^a   Slone, Robert V ^a   Watson, David F ^a   Carrell, Thomas G ^a  

^a NORTHWESTERN UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

IMINE; ION; LIGAND; METAL; NANOPARTICLE; ZEOLITE;

ARTICLE; CRYSTAL STRUCTURE; ELECTROCHEMICAL ANALYSIS; FILM; ION TRANSPORT; ISOMER; MEMBRANE PERMEABILITY; MEMBRANE TRANSPORT; POROSITY; TRANSPORT KINETICS;

EID: 0033608098     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9829867     Document Type: Article

References (69)

1. Fujita, M.; Yakazi, J.; Ogura, K. J. Am. Chem. Soc. 1990, 112, 5645.
2. Fujita, M.; Yakazi, J.; Ogura, K.; Ogura, K. Tetrahedron Lett. 1991, 32, 5589.
3. Fujita, T.; Sasaki, O.; Mitsuhashi, T.; Fujita, T.; Yagazi, J.; Yamaguchi, K.; Ogura, K. J. Chem. Soc., Chem. Commun. 1996, 1535.
4. Stang, P.; Olenyuk, B. Acc. Chem. Res. 1997, 30, 502 and references therein.
5. Slone, R. V.; Yoon, D. I.; Calhoun, R. M.; Hupp, J. T. J. Am. Chem. Soc. 1995, 117, 11813.
6. Slone, R. V.; Hupp, J. T.; Stern, C. L.; Albrecht-Schmitt, T. E. Inorg. Chem. 1996, 35, 4096.
7. Slone, R. V.; Hupp, J. T. Inorg. Chem. 1997, 36, 5422.
8. Leung, W.-H.; Cheng, J. Y. K.; Hun, T. S. M.; Che, C.-M., Wong, W.-T.; Cheung, K. K., Organometallics 1996, 15, 1497.
9. Kalb, W. C.; Demidowicz, Z.; Speckmann, D. M.; Knobler, C.; Teller, R. G.; Hawthorne, M. F. Inorg. Chem. 1982, 21, 4027.
10. Stricken, P. M.; Volcko, E. J.; Verkade, J. G. Inorg. Chem. 1983, 105, 2494.
11. Rauter, H.; Hillgeris, E. C.; Erxleben, A.; Lippert, B. J. Am. Chem. Soc. 1994, 116, 616.
12. Olenyuk, B.; Whiteford, J. A.; Stang, P. J. J. Am. Chem. Soc. 1996, 118, 8221.
13. Slone, R. V.; Benkstein, K. D.; Bélanger, S.; Hupp, J. T.; Guzei, I. A.; Rheingold, A. L. Coord. Chem. Rev. 1998, 171 (1), 221.
14. Fujita, M.; Nagao, S.; Iida, M.; Ogata, K. J. Am. Chem. Soc. 1993, 115, 1574.
15. Stang, P. J.; Cao, D. H.; Saito, S.; Arif, A. M. J. Am. Chem. Soc. 1995, 117, 6273.
16. Stang, P. J.; Cao, D. H. J. Am. Chem. Soc. 1994, 116, 4981.
17. Fujita, M.; Nagao, S.; Ogura, K. J. Am. Chem. Soc. 1995, 117, 1649.
18. See also: Beer, P. D. J. Chem. Soc., Chem. Commun. 1996, 689.
19. Stang, P. J.; Cao, D. H.; Chen, K.; Gray, G. M.; Muddiman, D. C.; Smith, R. D. J. Am. Chem. Soc. 1997, 119. 5163.
20. For elegant illustrations of such applications with mesoporous membranes of a different type (metal and carbon nanotubules), see: (a) Nishizawa, M.; Menon, V. P.; Martin, C. R. Science 1995, 268, 700. (b) Jirage, K. B.; Hulteen. J. C.; Martin, C. R. Science 1997, 278, 655. (c) Che, G.; Fisher, E. R.; Martin, C. R. Nature 1998, 393, 346.
21. For elegant illustrations of such applications with mesoporous membranes of a different type (metal and carbon nanotubules), see: (a) Nishizawa, M.; Menon, V. P.; Martin, C. R. Science 1995, 268, 700. (b) Jirage, K. B.; Hulteen. J. C.; Martin, C. R. Science 1997, 278, 655. (c) Che, G.; Fisher, E. R.; Martin, C. R. Nature 1998, 393, 346.
22. For elegant illustrations of such applications with mesoporous membranes of a different type (metal and carbon nanotubules), see: (a) Nishizawa, M.; Menon, V. P.; Martin, C. R. Science 1995, 268, 700. (b) Jirage, K. B.; Hulteen. J. C.; Martin, C. R. Science 1997, 278, 655. (c) Che, G.; Fisher, E. R.; Martin, C. R. Nature 1998, 393, 346.
23. For representative reports on gated charge transport through polymeric thin films and electrode-supported monolayers. respectively. see: (a) Burgmayer, P.; Murray, R. W. J. Am. Chem. Soc. 1982, 104, 6139. Burgmayer, P.; Murray, R. W. J. Electroanal. Chem. 1983, 147, 339. Burgmayer, P.; Murray, R. W. J. Phys. Chem. 1984, 88, 2515. (b) Campbell, D.; Herr, B. R.; Hulteen, J. C.; VanDuyne, R. P.; Mirkin, C. A. J. Am. Chem. Soc. 1996, 118, 10211.
24. For representative reports on gated charge transport through polymeric thin films and electrode-supported monolayers. respectively. see: (a) Burgmayer, P.; Murray, R. W. J. Am. Chem. Soc. 1982, 104, 6139. Burgmayer, P.; Murray, R. W. J. Electroanal. Chem. 1983, 147, 339. Burgmayer, P.; Murray, R. W. J. Phys. Chem. 1984, 88, 2515. (b) Campbell, D.; Herr, B. R.; Hulteen, J. C.; VanDuyne, R. P.; Mirkin, C. A. J. Am. Chem. Soc. 1996, 118, 10211.
25. For representative reports on gated charge transport through polymeric thin films and electrode-supported monolayers. respectively. see: (a) Burgmayer, P.; Murray, R. W. J. Am. Chem. Soc. 1982, 104, 6139. Burgmayer, P.; Murray, R. W. J. Electroanal. Chem. 1983, 147, 339. Burgmayer, P.; Murray, R. W. J. Phys. Chem. 1984, 88, 2515. (b) Campbell, D.; Herr, B. R.; Hulteen, J. C.; VanDuyne, R. P.; Mirkin, C. A. J. Am. Chem. Soc. 1996, 118, 10211.
26. For representative reports on gated charge transport through polymeric thin films and electrode-supported monolayers. respectively. see: (a) Burgmayer, P.; Murray, R. W. J. Am. Chem. Soc. 1982, 104, 6139. Burgmayer, P.; Murray, R. W. J. Electroanal. Chem. 1983, 147, 339. Burgmayer, P.; Murray, R. W. J. Phys. Chem. 1984, 88, 2515. (b) Campbell, D.; Herr, B. R.; Hulteen, J. C.; VanDuyne, R. P.; Mirkin, C. A. J. Am. Chem. Soc. 1996, 118, 10211.
27. Baker, R. W.; Cussler, E. L.; Eykamp, W.; Koros, W. J.; Riley, R. T.; Strathmann, H. Membrane Separations Systems, Recent Developments and Future Directions; Noyes Data Corp.: Park Ridge, IL, 1991.
28. Stang, P. J.; Chen, K.; Arif, A. M. J. Am. Chem, Soc. 1995, 117, 8783.
29. Whiteford, J. A.; Lu, C. V.; Stang, P. J. J. Am. Chem. Soc. 1997, 119, 2524.
30. The requirement can be circumvented, of course, if defects (holes) exist, if permeant redox self-exchange reactions are significant, or if the film itself becomes electronically conductive.
31. 205
32. Ohnuki, Y.; Matsuda, H.; Ohsaka, T.; Oyama, N. J. Electroanal. Chem. 1983, 158, 55.
33. Ohsaka, T.; Hirokawa, T.; Miyamoto, H.; Oyama, N. Anal. Chem. 1987, 59, 1758.
34. Taj, S.; Ahmed, M F., Sankarapapavinasam, S. Ind. J. Chem. 1993, 32A, 521.
35. McCarley, R. L.; Irene, E. A.; Murray, R. W. J. Phys. Chem. 1991, 95, 2492.
36. Ikeda, T.; Schmehl, R.; Denisevidch, P.; Willman, K.; Murray, R. W. J. Am. Chem. Soc. 1982, 104, 2683.
37. Gough, S.; Strouse, G. F.; Meyer, T. J.; Sullivan, B. P. Inorg. Chem. 1991, 30, 2942.
38. Gould, S.; Meyer, T. J. J. Am. Chem. Soc. 1991, 113, 7442.
39. Pressprich, K. A.; Maybury, S. G.; Thomas, R. E.; Limon, R. W.; Irene, E. A.; Murray, R. W. J. Phys. Chem. 1989, 93, 5568.
40. Bélanger, S.; Stevenson, K. J.; Mudhaka, S. A.; Hupp, J. T. Langmuir, submitted.
41. Van, S. G.; Hupp, J. T. J. Electroanal. Chem. 1995, 397, 119.
42. Cosnier, S.; Deronzier, A.; Roland, J.-F. J. Electroanal. Chem. 1991, 310, 71.
43. Lyon, L. A.; Ratner, M. A., Hupp, J. T. J. Electroanal. Chem. 1995, 387, 109.
44. Ghadiri, M. R.; Granja, J. R.; Buehler, L. K. Nature 1994, 369, 301.
45. Granja, J. R.; Ghadiri, M. R. J. Am. Chem. Soc. 1994, 116, 10785.
46. Hartgerink, J. D.; Clark, T. D.; Ghadiri, M. R. Chem. Eur. J. 1998, 4, 1367.
47. Giordano, P. J.; Wrighton, M. S. J. Am. Chem. Soc. 1979, 101, 2888.
48. Wheeler, S. H.; Zingheim, S. C.; Nathan, L. C. J. Inorg. Nucl. Chem. 1978, 40, 779.
49. Curtis, J. C.; Sullivan, B. P.; Meyer, T. J. Inorg. Chem. 1983, 22, 224.
50. de Meulenaer, J.; Tompa, H. Acta Crystallogr. 1965, 19, 1014.
51. Sheldrick, G. M. In Crystallographic Computing 3; Sheldrick G. M., Kruger, C., Goddard, R., Eds.; Oxford University Press: New York, 1985; p 175.
52. International Tables for Crystallography; Kynoch Press: Witton, Birmingham, U.K., 1992; Vol. C, tables 4.2.6.8 and 6.1.1.1.
53. teXsan. Single-Crystal Structure Analysis Software. Version 1.7.MSC. Molecular Structure Corp. 3200 Research Forest Drive, The Woodlands, TX, 1995.
54. Bélanger, S.; Hupp, J. T.; Stern, C. L. Acta Crystallogr. 1998, C54, 1596.
55. Keefe, M. H. unpublished results.
56. The one-electron oxidation of Re(I) is observed in solution at potentials higher that 1.3 V vs SSCE, and a one-electron ligand-based reduction is present below -0.9 V vs SSCE (see ref 13). The molecular squares are electrochemically silent in the potential range investigated here, and no interfering signal from the squares is observed.
57. 4- complex is size-excluded, rather than excluded on the basis of its large negative charge, by showing that the small, but highly charged ferricyanide anion does in fact permeate under analogous conditions.
58. Note that the effective size of the cavity is smaller than the Re⋯Re distance, because of the tilt of the bridging rings relative to the square cavity walls and because of finite van der Waals radii. Note that the effective diffusion coefficients of nonspherical molecules in solution are proportional to their average diameters (see: Koval, C. A.; Ketterer, M. E.; Reidsema, C. M. J. Phys. Chem. 1986, 90, 4201.) In thin-film materials, the permeant molecule could, in principle, rotate faster than it diffuses (i.e., the film could exhibit shape selectivity if the molecule can tumble fast enough for the permeation to be dominated by the smallest molecular dimension).
59. Although we cannot absolutely exclude the alternative intermolecular permeation pathway, it is unlikely that the size cutoff for permeation between molecular squares would vary with the molecular squares' dimensions. Furthermore, quantitative data on the comer molecule 4 (where permeation is expected to take place mainly through such intermolecular pathways) show that permeation via this mechanism is at least 1 order of magnitude lower than for the parent square 2.
60. Stevenson, K. J.; Bélanger, S., unpublished studies.
61. Gough, D. A.; Leypoldt, J. K. Anal. Chem. 1979, 51, 439.
62. Leddy, J. A.; Bard, A. J. J. Electroanal. Chem. Interfacial Electrochem. 1983, 15, 223.
63. Ewing, A. G.; Feldman, B. J.; Murray, R. W. J. Phys. Chem. 1985, 89, 1263.
64. Savéant, J.-M. J. Electroanal. Chem. 1991, 502, 91.
65. The experiment with 4 was carried out in pH 8 buffer to ensure that the free pyridine site on the 4,4′-bpy ligand remained unprotonated. Protonation of this site would lead to a cationic film, which could exclude the Ru permeant-based ion charge (not size). Additional experiments (not shown) on the 4-phenylpyridine analogue 5, where the free pyridine ring of the 4,4′-bpy ligand is replaced by a (pH-independent) phenyl ring, revealed similar transport blocking behavior.
66. film value is the average value based on measurements with eight films in the 0.4-2.2-μm thickness range.
67. Pinhole defects are comparatively more important with thinner films: the thinnest low-defect-density films currently available using evaporative casting are 0.15 μm.
68. 2+).
69. film values obtained here to values obtained for similarly sized neutral permeants in charged framework metallopolymeric films, where electrostatic effects should be absent, still indicates a roughly 1 order of magnitude greater permeability for the metallocyclophane-derived materials.