Cooperative Assembly of Discrete Stacked Aggregates Driven by Supramolecular Host鈥揋uest Complexation

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• 作者：Nuno Bas铆lio ; 脕ngel Pi帽eiro ; Jos茅 P. Da Silva ; Luis Garc铆a-R铆o
• 刊名：Journal of Organic Chemistry
• 出版年：2013
• 出版时间：September 20, 2013
• 年：2013
• 卷：78
• 期：18
• 页码：9113-9119
• 全文大小：319K
• 年卷期：v.78,no.18(September 20, 2013)
• ISSN：1520-6904

文摘

p-Sulfonatocalix[4]arene (SC4) interacts with the aromatic dye crystal violet (CV) to form complexes with stoichiometries ranging from SC4:CV = 1:1 up to 1:5 both in solution and in the gas phase. While the 1:1 complex is of the inclusion type, as frequently observed for other guests, in the higher-order complexes the CV molecules interact with SC4 in a peripheral manner. The formation of such complexes is driven by ionic interactions established between the dye and the calixarene and by CV鈥揅V stacking interactions. The application of an advanced fitting procedure made possible a quantitative analysis of the UV鈥搗is data and allowed the determination of the stepwise binding constants. This unprecedented approach provides evidence that the formation of the highest-order complexes occurs through a cooperative mechanism. Moreover, the development of a quantitative analytical model enables the possibility of using this type of system for water-soluble sensing assays, as is also exemplified in the present work.