Sterically Controlled Architectural Reversion in Hydrogen-Bonded Crystalline Clathrates

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• 作者：Cara C. Evans ; Lisa Sukarto ; and Michael D. Ward
• 刊名：Journal of the American Chemical Society
• 出版年：1999
• 出版时间：January 20, 1999
• 年：1999
• 卷：121
• 期：2
• 页码：320 - 325
• 全文大小：189K
• 年卷期：v.121,no.2(January 20, 1999)
• ISSN：1520-5126

文摘

Guanidinium cations and azobenzene-4,4'-disulfonate (ABDS) dianions form a host lattice with abilayer architecture in the presence of 1,4-dibromobenzene (DBB), 1,4-divinylbenzene (DVB), 1-nitronaphthalene(NN), and nitrobenzene (NB) guest molecules. The guests occupy one-dimensional pores in bilayer galleriescreated by ABDS dianions, which behave as "pillars" that connect opposing hydrogen-bonded guanidinium-sulfonate (GS) sheets. This contrasts with our previous observation of a high porosity "brick" framework thatcrystallized with these guests when the pillar was biphenyl-4,4'-disulfonate (BPDS). The reversion to thebilayer framework upon changing to ABDS can be attributed to the increased length of this pillar. Whereasthe four guests are too large to fit in the pores of an ideal bilayer framework constructed from BPDS, they canbe accommodated in bilayer galleries of increased height provided by the longer ABDS pillars. The control offramework architecture in this manner demonstrates that the solid-state structure of these materials can berationally manipulated by systematic, stepwise adjustments to the size of the host components and of theguests. The ability to tune the pore volume of these frameworks so that different guests can be included, whileretaining the essential structural features of the GS hosts, provides a versatile route to the synthesis of functionalclathrates.