Inorganic鈥揙rganic Hybrid Vesicles with Counterion- and pH-Controlled Fluorescent Properties

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• 作者：Dong Li ; Jie Song ; Panchao Yin ; Silas Simotwo ; Andrew J. Bassler ; YuYu Aung ; James E. Roberts ; Kenneth I. Hardcastle ; Craig L. Hill ; Tianbo Liu
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：September 7, 2011
• 年：2011
• 卷：133
• 期：35
• 页码：14010-14016
• 全文大小：961K
• 年卷期：v.133,no.35(September 7, 2011)
• ISSN：1520-5126

文摘

Two inorganic鈥搊rganic hybrid clusters with one or two covalently linked pyrene fluorescent probes, [(n-C₄H₉)₄N]₂[V₆O₁₃{(OCH₂)₃C(NH(CO)CH₂CH₂CH₂C₁₆H₉)}{(OCH₂)₃C鈥?NH₂)}] ((TBA⁺)₂1) and [(n-C₄H₉)₄N]₂[V₆O₁₃{(OCH₂)₃C(NH(CO)CH₂CH₂CH₂C₁₆H₉)}₂] ((TBA⁺)₂2), respectively, are synthesized from Lindqvist type polyoxometalates (POMs). The incorporation of pyrene into POMs results in amphiphilic hybrid molecules and simultaneously offers a great opportunity to study the interaction between hybrid clusters and their counterions. 2D-NOESY NMR and fluorescence techniques have been used to study the role of counterions such as tetrabutyl ammonium (TBA) in the vesicle formation of the hybrid clusters. The TBA⁺ ions not only screen the electrostatic repulsions between the POM head groups but also are involved in the hydrophobic region of the vesicular structure where they interrupt the formation of pyrene excimers that greatly perturbs the luminescence signal from the vesicle solution. By replacing the TBA⁺ counterions with protons, the new vesicles demonstrate interesting pH-dependent fluorescence properties.