Chain Entropy Beats Hydrogen Bonds to Unfold and Thread Dialcohol Phosphates inside Cyanostar Macrocycles To Form [3]Pseudorotaxanes
- Rachel E. FadlerRachel E. FadlerDepartment of Chemistry, Indiana University, Bloomington, Indiana 47405, United StatesMore by Rachel E. Fadler
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- Abdelaziz Al OuahabiAbdelaziz Al OuahabiUniversité de Strasbourg, CNRS, Institut Charles Sadron UPR22, Strasbourg, 67034, FranceMore by Abdelaziz Al Ouahabi
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- Bo QiaoBo QiaoDepartment of Chemistry, Indiana University, Bloomington, Indiana 47405, United StatesMore by Bo Qiao
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- Veronica CartaVeronica CartaDepartment of Chemistry, Indiana University, Bloomington, Indiana 47405, United StatesMore by Veronica Carta
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- Niklas F. KönigNiklas F. KönigUniversité de Strasbourg, CNRS, Institut Charles Sadron UPR22, Strasbourg, 67034, FranceMore by Niklas F. König
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- Xinfeng GaoXinfeng GaoDepartment of Chemistry, Indiana University, Bloomington, Indiana 47405, United StatesMore by Xinfeng Gao
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- Wei ZhaoWei ZhaoDepartment of Chemistry, Indiana University, Bloomington, Indiana 47405, United StatesMore by Wei Zhao
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- Yankai ZhangYankai ZhangUniversité de Strasbourg, CNRS, Institut Charles Sadron UPR22, Strasbourg, 67034, FranceMore by Yankai Zhang
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- Jean-François LutzJean-François LutzUniversité de Strasbourg, CNRS, Institut Charles Sadron UPR22, Strasbourg, 67034, FranceMore by Jean-François Lutz
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- Amar H. Flood*Amar H. Flood*Email: [email protected]Department of Chemistry, Indiana University, Bloomington, Indiana 47405, United StatesMore by Amar H. Flood
Abstract
The recognition of substituted phosphates underpins many processes including DNA binding, enantioselective catalysis, and recently template-directed rotaxane synthesis. Beyond ATP and a few commercial substrates, however, little is known about how substituents effect organophosphate recognition. Here, we examined alcohol substituents and their impact on recognition by cyanostar macrocycles. The organophosphates were disubstituted by alcohols of various chain lengths, dipropanol, dihexanol, and didecanol phosphate, each accessed using modular solid-phases syntheses. Based on the known size-selective binding of phosphates by π-stacked dimers of cyanostars, threaded [3]pseudorotaxanes were anticipated. While seen with butyl substituents, pseudorotaxane formation was disrupted by competitive OH···O– hydrogen bonding between both terminal hydroxyls and the anionic phosphate unit. Crystallography also showed formation of a backfolded propanol conformation resulting in an 8-membered ring and a perched cyanostar assembly. Motivated by established entropic penalties accompanying ring formation, we reinstated [3]pseudorotaxanes by extending the size of the substituent to hexanol and decanol. Chain entropy overcomes the enthalpically favored OH···O– contacts to favor random-coil conformations required for seamless, high-fidelity threading of dihexanol and didecanol phosphates inside cyanostars. These studies highlight how chain length and functional groups on phosphate’s substituents can be powerful design tools to regulate binding and control assembly formation during phosphate recognition.
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