Chloride Anion Controlled Molecular "Switching". Binding of 2,5,7-Trinitro-9-dicyanomethylenefluorene-C60 by Tetrathiafulvalene Calix[4]pyrrole and Photophysical Generation of Two Different

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• 作者：Kent A. Nielsen ; Ginka H. Sarova ; Luis Mart&iacute ; n-Gomis ; Fernando Ferná ; ndez-Lá ; zaro ; Paul C. Stein ; Lionel Sanguinet ; Eric Levillain ; Jonathan L. Sessler ; Dirk M. Guldi ; Á ; ngela
• 刊名：Journal of the American Chemical Society
• 出版年：2008
• 出版时间：January 16, 2008
• 年：2008
• 卷：130
• 期：2
• 页码：460 - 462
• 全文大小：142K
• 年卷期：v.130,no.2(January 16, 2008)
• ISSN：1520-5126

文摘

The binding of the snake-like trinitrodicyanomethylenefluorene-C₆₀ derivative (TNDCF-C₆₀) to the dynamic receptor, tetrathiafulvalene calix[4]pyrrole (TTF-calix[4]pyrrole), may be controlled via the use of a chloride anion as an external trigger. Whereas, in the absence of a chloride anion, the TNDCF "tail" of the trinitrodicyanomethylenefluorene-C₆₀ substrate binds to the TTF-calix[4]pyrrole in a 2:1 (substrate/receptor) stoichiometry in CH₂Cl₂ solution, addition of a chloride anion (yellow) leads the TNDCF tail to be displaced in favor of a bound C₆₀ "head", a process that leads to the formation of a complex with overall 1:2:2 substrate/receptor/chloride anion stoichiometry. These chemical switching events are reflected in easy-to-visualize color changes, as well as in the production of two different kinds of charge-separated states following selective femtosecond photoexcitation.