Steric desolation enhances the effective molarities of intramolecular H-bonding interactions

Organic & Biomolecular Chemistry
Elena ChekmenevaSimon M Turega

Abstract

Free energy contributions due to intramolecular phosphonate diester-phenol H-bonds have been measured for 20 different supramolecular architectures in cyclohexanone solution. High throughput UV/Vis titrations were used in combination with chemical double mutant cycles to dissect out the contributions of different functional group interactions to the stabilities of over 100 different zinc porphyrin-pyridine ligand complexes. These complexes have previously been characterised in toluene and in 1,1,2,2-tetrachloroethane (TCE) solution. Intramolecular ester-phenol H-bonds that were measured in these less polar solvents are too weak to be detected in cyclohexanone, which is a more competitive solvent. The stability of the intermolecular phosphonate diester-phenol H-bond in cyclohexanone is an order of magnitude lower than in TCE and two orders of magnitude lower than in toluene. As a consequence, only seven of the twenty intramolecular phosphonate diester-phenol interactions that were previously measured in toluene and TCE could be detected in cyclohexanone. The effective molarities (EM) for these intramolecular interactions are different in all three solvents. Determination of the EM accounts for solvent effects on the strengths of...Continue Reading

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Citations

May 4, 2017·Journal of the American Chemical Society·Stefan HenkelChristopher A Hunter
Mar 1, 2016·Chemical Science·Giulia IadevaiaChristopher A Hunter
Jan 21, 2014·Organic & Biomolecular Chemistry·Michael A JinksChristopher A Hunter
Jan 1, 2016·Chemical Science·Alexander E StrossChristopher A Hunter
Sep 1, 2016·Chemical Science·Alexander E StrossChristopher A Hunter
Jan 31, 2013·Journal of the American Chemical Society·Harry AdamsSimon M Turega
May 21, 2014·Journal of the American Chemical Society·Simon TuregaMichael D Ward
Aug 24, 2013·Journal of the American Chemical Society·Hongmei SunSimon Turega
Dec 10, 2016·Journal of the American Chemical Society·Thomas A HubbardScott L Cockroft

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