Structural Characterization of Crystalline Ternary Inclusion Compounds at the Air-Water Interface
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- 作者：David J. Plaut ; Stephen M. Martin ; Kristian Kjaer ; Markus J. Weygand ; Meir Lahav ; Leslie Leiserowitz ; Isabelle Weissbuch ; and Michael D. Ward
- 刊名：Journal of the American Chemical Society
- 出版年：2003
- 出版时间：December 24, 2003
- 年：2003
- 卷：125
- 期：51
- 页码：15922 - 15934
- 全文大小：598K
- 年卷期：v.125,no.51(December 24, 2003)
- ISSN：1520-5126
文摘
Crystalline ternary inclusion monolayers consisting of a two-dimensional hydrogen-bonded hostnetwork of guanidinium (G) ions and organosulfonate (S) amphiphiles, and biphenylalkane guests, can begenerated at the air-water interface through synergistic structural enforcement by hydrogen bonding andhost-guest packing. Surface pressure-area isotherms of the 4'-hexadecylbiphenyl-4-sulfonate (C16BPS)amphiphile in the presence of G, with or without guest, are characterized by lift-off molecular areas expectedfor the GS sheet based on single-crystal X-ray structures of homologous bulk crystals. Intercalation ofbiphenylalkane guests (4-CnH2n+1-C6H4-C6H5, n = 1, 4, 6, 10, 16; denoted CnBP) between organosulfonatehydrophobes, which define pocketlike cavities in the GS monolayer host, afford ternary inclusion monolayerswith a 1:1 host-guest stoichiometry. These inclusion monolayers are less compressible than the guest-free host, consistent with dense packing of the biphenylalkane moieties of the host and the biphenylalkaneguests. The inclusion monolayers are distinguished from the amorphous guest-free host and from selectedguanidinium-free mixed monolayers by structural characterization with grazing-angle incidence X-raydiffraction (GIXD). The GIXD data for the ternary (G)C16BPS:C16BP and (G)C16BPS:C6BP inclusionmonolayers obtained upon compression are consistent with a rectangular unit cell. The dimensions of theseunit cells and refinement of the GIXD data suggest a "rotated shifted ribbon" GS hydrogen-bonding motifsimilar to that observed in some bulk GS crystals, including (G)(ethylbiphenylsulfonate). GIXD reveals that(G)C16BPS:C16BP and (G)C16BPS:C6BP are more crystalline than the corresponding guanidinium-freemixed monolayers. The (G)C16BPS:C6BP inclusion monolayer is stable upon compression, even thoughthe alkyl-alkyl host-guest interactions are reduced due to the shorter hexyl substituents of the guest,demonstrating an important reinforcing role for the hydrogen-bonded GS sheet. The structure of a C16BPS:tetracosane (C24) mixed monolayer is independent of G; the unit cell symmetry and dimensions suggesta structure governed by alkyl-alkane interactions that prohibit formation of a GS network. These resultsillustrate that the existence of ternary inclusion monolayers with an intact GS network requires guestmolecules that are structurally homologous with the hydrophobes of the host, in this case biphenylalkanes.The observation of these inclusion compounds suggests an approach for introducing functional nonamphiphilic molecules to an air-water interface through inclusion in a well-defined host.