Crystal Growth of Extended Solids by Nonaqueous Gel Diffusion

Chemistry of Materials

Volumn 9, Issue 5, 1997, Pages 1074-1076

  Yaghi, O M ^a   Li, Guangming ^a   Li, Hailian ^a  

^a ARIZONA STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001057887     PISSN: 08974756     EISSN: None     Source Type: Journal    
DOI: 10.1021/cm970069e     Document Type: Article

References (37)

1. (a) For example: copper metal crystals were obtained by chemical reduction of copper sulfate that has been incorporated in gel: Holmes, H. N. Colloide Chemistry; Alexander, J., Ed.; Chemical Catalog Co.: New York, 1926. Dendritic crystals of lead were found in a gel containing lead acetate and metallic zinc: Simon, A. L. Kolloid Z. 1913, 12, 171. (b) Henisch, H. K. Crystals in Gels and Liesegang Rings; Cambridge University Press: Cambridge, 1988. McCauley, J. W.; Roy, R. Am. Mineral. 1974, 59, 947. Holmes, H. N. J. Franklin Inst. 1917, 184, 743. (e) Cody, A. M.; Horner, H. T.; Cody, R. D. In Scanning Electron Microscopy; SEM Inc.: AMF O'Hare, Chicago, IL, 1982. (f) Suib, S. L. J. Chem. Educ. 1985 62, 81.
2. (a) For example: copper metal crystals were obtained by chemical reduction of copper sulfate that has been incorporated in gel: Holmes, H. N. Colloide Chemistry; Alexander, J., Ed.; Chemical Catalog Co.: New York, 1926. Dendritic crystals of lead were found in a gel containing lead acetate and metallic zinc: Simon, A. L. Kolloid Z. 1913, 12, 171. (b) Henisch, H. K. Crystals in Gels and Liesegang Rings; Cambridge University Press: Cambridge, 1988. McCauley, J. W.; Roy, R. Am. Mineral. 1974, 59, 947. Holmes, H. N. J. Franklin Inst. 1917, 184, 743. (e) Cody, A. M.; Horner, H. T.; Cody, R. D. In Scanning Electron Microscopy; SEM Inc.: AMF O'Hare, Chicago, IL, 1982. (f) Suib, S. L. J. Chem. Educ. 1985 62, 81.
3. (a) For example: copper metal crystals were obtained by chemical reduction of copper sulfate that has been incorporated in gel: Holmes, H. N. Colloide Chemistry; Alexander, J., Ed.; Chemical Catalog Co.: New York, 1926. Dendritic crystals of lead were found in a gel containing lead acetate and metallic zinc: Simon, A. L. Kolloid Z. 1913, 12, 171. (b) Henisch, H. K. Crystals in Gels and Liesegang Rings; Cambridge University Press: Cambridge, 1988. McCauley, J. W.; Roy, R. Am. Mineral. 1974, 59, 947. Holmes, H. N. J. Franklin Inst. 1917, 184, 743. (e) Cody, A. M.; Horner, H. T.; Cody, R. D. In Scanning Electron Microscopy; SEM Inc.: AMF O'Hare, Chicago, IL, 1982. (f) Suib, S. L. J. Chem. Educ. 1985 62, 81.
4. (a) For example: copper metal crystals were obtained by chemical reduction of copper sulfate that has been incorporated in gel: Holmes, H. N. Colloide Chemistry; Alexander, J., Ed.; Chemical Catalog Co.: New York, 1926. Dendritic crystals of lead were found in a gel containing lead acetate and metallic zinc: Simon, A. L. Kolloid Z. 1913, 12, 171. (b) Henisch, H. K. Crystals in Gels and Liesegang Rings; Cambridge University Press: Cambridge, 1988. McCauley, J. W.; Roy, R. Am. Mineral. 1974, 59, 947. Holmes, H. N. J. Franklin Inst. 1917, 184, 743. (e) Cody, A. M.; Horner, H. T.; Cody, R. D. In Scanning Electron Microscopy; SEM Inc.: AMF O'Hare, Chicago, IL, 1982. (f) Suib, S. L. J. Chem. Educ. 1985 62, 81.
5. (a) For example: copper metal crystals were obtained by chemical reduction of copper sulfate that has been incorporated in gel: Holmes, H. N. Colloide Chemistry; Alexander, J., Ed.; Chemical Catalog Co.: New York, 1926. Dendritic crystals of lead were found in a gel containing lead acetate and metallic zinc: Simon, A. L. Kolloid Z. 1913, 12, 171. (b) Henisch, H. K. Crystals in Gels and Liesegang Rings; Cambridge University Press: Cambridge, 1988. McCauley, J. W.; Roy, R. Am. Mineral. 1974, 59, 947. Holmes, H. N. J. Franklin Inst. 1917, 184, 743. (e) Cody, A. M.; Horner, H. T.; Cody, R. D. In Scanning Electron Microscopy; SEM Inc.: AMF O'Hare, Chicago, IL, 1982. (f) Suib, S. L. J. Chem. Educ. 1985 62, 81.
6. (a) For example: copper metal crystals were obtained by chemical reduction of copper sulfate that has been incorporated in gel: Holmes, H. N. Colloide Chemistry; Alexander, J., Ed.; Chemical Catalog Co.: New York, 1926. Dendritic crystals of lead were found in a gel containing lead acetate and metallic zinc: Simon, A. L. Kolloid Z. 1913, 12, 171. (b) Henisch, H. K. Crystals in Gels and Liesegang Rings; Cambridge University Press: Cambridge, 1988. McCauley, J. W.; Roy, R. Am. Mineral. 1974, 59, 947. Holmes, H. N. J. Franklin Inst. 1917, 184, 743. (e) Cody, A. M.; Horner, H. T.; Cody, R. D. In Scanning Electron Microscopy; SEM Inc.: AMF O'Hare, Chicago, IL, 1982. (f) Suib, S. L. J. Chem. Educ. 1985 62, 81.
7. (a) For example: copper metal crystals were obtained by chemical reduction of copper sulfate that has been incorporated in gel: Holmes, H. N. Colloide Chemistry; Alexander, J., Ed.; Chemical Catalog Co.: New York, 1926. Dendritic crystals of lead were found in a gel containing lead acetate and metallic zinc: Simon, A. L. Kolloid Z. 1913, 12, 171. (b) Henisch, H. K. Crystals in Gels and Liesegang Rings; Cambridge University Press: Cambridge, 1988. McCauley, J. W.; Roy, R. Am. Mineral. 1974, 59, 947. Holmes, H. N. J. Franklin Inst. 1917, 184, 743. (e) Cody, A. M.; Horner, H. T.; Cody, R. D. In Scanning Electron Microscopy; SEM Inc.: AMF O'Hare, Chicago, IL, 1982. (f) Suib, S. L. J. Chem. Educ. 1985 62, 81.
8. (a) Brinker, C. J.; Scherer, G. W. Sol - Gel Science: The Physics and Chemistry of Sol - Gel Processing; Academic Press: San Diego, CA, 1990.
9. (b) Nanophase Materials: Synthesis-Properties-Applications; Hadjipanayis, G. C., Siegal, R. W., Eds.; NATO ASI Series E.: Applied Sciences; Kluwer Publishers: Dordrecht, The Netherlands, 1994; Vol. 260.
10. Biomineralization: Chemical and Biological Perspectives; Mann, S., Webb, J., Williams, R. J. P., Eds.; VCH Publishers: New York, 1989.
11. Large crystals of molecular organic compounds have been successfully obtained from nonaqueous gels. For example: (a) 2-phenyl-1,4-hydroquinone-2-phenyl-1,4-benzoquinone complex; grown using Sephadex LH-20 (alkylated cross-linked dextran) gel in aromatic hydrocarbons: Desiraju, G. R.; Curtin, D. Y.; Paul I. C. J. Am. Chem. Soc. 1977, 99, 6148. Also see: (b) phenol-benzoquinone complex: Sakurai, T. Acta Crystallogr. 1968, B24, 403. Harding, T. T.; Wallwork, S. C. Acta Crystallogr. 1952, 6, 791. Naphthalene-picric acid: Baddar, F. G.; Mikhail, H. J. Chem. Soc. 1949, 2927.
12. Large crystals of molecular organic compounds have been successfully obtained from nonaqueous gels. For example: (a) 2-phenyl-1,4-hydroquinone-2-phenyl-1,4-benzoquinone complex; grown using Sephadex LH-20 (alkylated cross-linked dextran) gel in aromatic hydrocarbons: Desiraju, G. R.; Curtin, D. Y.; Paul I. C. J. Am. Chem. Soc. 1977, 99, 6148. Also see: (b) phenol-benzoquinone complex: Sakurai, T. Acta Crystallogr. 1968, B24, 403. Harding, T. T.; Wallwork, S. C. Acta Crystallogr. 1952, 6, 791. Naphthalene-picric acid: Baddar, F. G.; Mikhail, H. J. Chem. Soc. 1949, 2927.
13. Large crystals of molecular organic compounds have been successfully obtained from nonaqueous gels. For example: (a) 2-phenyl-1,4-hydroquinone-2-phenyl-1,4-benzoquinone complex; grown using Sephadex LH-20 (alkylated cross-linked dextran) gel in aromatic hydrocarbons: Desiraju, G. R.; Curtin, D. Y.; Paul I. C. J. Am. Chem. Soc. 1977, 99, 6148. Also see: (b) phenol-benzoquinone complex: Sakurai, T. Acta Crystallogr. 1968, B24, 403. Harding, T. T.; Wallwork, S. C. Acta Crystallogr. 1952, 6, 791. Naphthalene-picric acid: Baddar, F. G.; Mikhail, H. J. Chem. Soc. 1949, 2927.
14. Large crystals of molecular organic compounds have been successfully obtained from nonaqueous gels. For example: (a) 2-phenyl-1,4-hydroquinone-2-phenyl-1,4-benzoquinone complex; grown using Sephadex LH-20 (alkylated cross-linked dextran) gel in aromatic hydrocarbons: Desiraju, G. R.; Curtin, D. Y.; Paul I. C. J. Am. Chem. Soc. 1977, 99, 6148. Also see: (b) phenol-benzoquinone complex: Sakurai, T. Acta Crystallogr. 1968, B24, 403. Harding, T. T.; Wallwork, S. C. Acta Crystallogr. 1952, 6, 791. Naphthalene-picric acid: Baddar, F. G.; Mikhail, H. J. Chem. Soc. 1949, 2927.
15. (a) Atwood, J. L., MacNicol, D. D., Davies, J. E. D., Vogtle, F., Lehn, J.-M., Eds. Comprehensive Supramolecular Chemistry; Pergamon: Oxford, 1996; Vol. 1-10.
16. (b) Stein, A.; Keller, S. W.; Mallouk, T. E. Science 1993, 259, 1558.
17. Fagan, P. J.; Ward, M. D. Sci. Am. 1992, 267, 48.
18. Bein, T., Ed. Supramolecular Architecture: Synthetic Control in Thin Films and Solids; American Chemical Society: Washington, DC, 1992.
19. (e) Dagai, R. Chem. Eng. News 1991, 69, 24-30.
20. (a) Day, V. W.; Klemperer, W. G.; Mainz, V. V.; Millar, D. M. J. Am. Chem. Soc. 1985, 107, 8262.
21. (b) Agaskar, P. A.; Day, V. W.; Klemperer, W. G. J. Am. Chem. Soc. 1987, 109, 5554.
22. Although PEO polymeric matrixes have been used to study the complexation of metals ions and to prepare nanocrystals of extended inorganic solids (Iwamoto, R.; Saito, Y.; Ishihara, H.; Tadokoro, H. J. Polym. Sci. 1968, 6, 1509. Bianconi, P. A.; Lin, J.; Strzelecki, A. R. Nature 1991, 349, 315), we are not aware of reports of their use for the preparation of large single crystals of extended covalent solids.
23. Although PEO polymeric matrixes have been used to study the complexation of metals ions and to prepare nanocrystals of extended inorganic solids (Iwamoto, R.; Saito, Y.; Ishihara, H.; Tadokoro, H. J. Polym. Sci. 1968, 6, 1509. Bianconi, P. A.; Lin, J.; Strzelecki, A. R. Nature 1991, 349, 315), we are not aware of reports of their use for the preparation of large single crystals of extended covalent solids.
24. (a) Yaghi, O. M.; Li, H.; Groy, T. L. J. Am. Chem. Soc. 1996, 118, 9096.
25. (b) Yaghi, O. M.; Li, G.; Li, H. Nature 1995, 378, 703-706.
26. Yaghi, O. M.; Davis, C. E.; Li, G.; Li, H. J. Am. Chem. Soc. 1997, 119, 2861.
27. Yaghi, O. M. In Access in Nanoporous Materials; Pinnavaia, T. J., Thorpe, M. F., Eds. Plenum: New York, 1995; p 111.
28. 7Zn: C, 52.79; H, 4.22; N, 5.86; Zn, 13.68. Found: C, 52.21; H, 4.19; N, 6.05; Zn, 13.09.
29. Holden, A.; Morrison, P. Crystals and Crystal Growing; MIT Press: Cambridge, 1982.
30. 3BTC (70.0 mg, 0.333 mmol) and pyridine (0.033 mL, 0.410 mmol) was layered above the gel and the tube covered with paraffin film then allowed to stand at room temperature for 4 days. Large block-shaped colorless crystals appeared just below the gel/solution interface. At this point, the solution and most of the gel surrounding the crystals were decanted using a pipet; then the crystals adhering to the inside surface of the tube were washed with absolute ethanol (2 × b mL) and collected on a medium frit.
31. XRPD data for the most prominent lines with d spacings in Å and the relative intensities placed in parentheses. Observed: 10.316 (100), 9.291 (76) 7.468 (50) 7.318 (48), 6.309 (28), 5.552 (44), 5.142 (39), 5.000 (58), 4.862 (37), 4.753 (39), 4.581 (42), 4.136 (96), 4.040 (60), 3.828 (36), 3.526 (31) 3.426 (56), 3.046 (23), 2.825 (29). Calculated: 10.274 (100), 9.248 (26), 7.448 (21), 6.308 (8), 5.713 (14), 5.200 (7), 5.021 (10), 4.863 (10), 4.624 (12), 4.183 (29), 4.049 (19), 3.820 (8), 3.536 (3), 3.451 (17), 3.192 (6), 2.826 (10).
32. 15
33. Even though, the process of growing such large crystals appears to be more of an art than a science, we learned that the task of determining the optimum conditions for crystal growth of metalorganic solids in PEO media is greatly simplified by consideration of these general guidelines: (a) The preparation of PEO gel or polymeric medium is best done in nonaqueous solvents such as methanol, ethanol, propanol, N,N-dimethylformamide, acetonitrile, and dimethyl sulfoxide, where 0.5 g of PEO (MW = 100 000) is mixed with approximately 2 mL of the desired solvent in the presence of 1,2-dichloroethane. (b) In some cases, it appears to be crucial that the layering solvent be the same as that used to prepare the solution containing the reagent to be impreganted into the gel. (c) The ligand or the metal ion may be used to impregnate the gel. (d) Using test tubes of the size mentioned above along with those volume proportions at room temperature appears to give high-quality crystals.
34. 1 (unweighted, based on F) = 0.045 for 1545 independent absorption-corrected reflections having 2θ(Mo Kα) < 45.8° and I > 3σ(I)} using counter-weighted, full-matrix, least-squares techniques and a structural model which incorporated anisotropic thermal parameters for all non-hydrogen and isotropic thermal parameters for all included hydrogen atoms.
35. (a) Desiraju, G. R. Crystal Engineering: The Design Of Organic Solids; Elsevier: New York, 1989; pp 115-173.
36. (b) Emsley, J. Chem. Soc. Rev. 1980, 91-124.
37. Semmington, D. Acta Chem. Scand. 1976, A30, 808.