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dc.creatorMenke A. J.
dc.creatorMellberg J. M.
dc.creatorPan H.
dc.creatorReibenspies J. H.
dc.creatorJanesko B. G.
dc.creatorSimanek E. E.
dc.date.accessioned2023-10-20T16:07:08Z
dc.date.available2023-10-20T16:07:08Z
dc.date.issued2023
dc.identifier.urihttps://doi.org/10.1002/chem.202300987
dc.identifier.urihttps://repository.tcu.edu/handle/116099117/61271
dc.description.abstractHinge motion is observed in macrocyclic, mortise-type molecular hinges using variable temperature NMR spectroscopy. The data is consistent with dynamic hinging from a folded-to-extended-to-folded enantiomeric state. Crystallographic and solution structures of the folded states are reported. Chemical shift predictions derived from crystallographic data corroborate fully revolute hinge motion. The rate of hinging is affected by steric congestion at the hinge axis. A macrocycle containing glycine, 1, hinges faster than one comprising aminoisobutyric acid, 2. The free energies of activation, ?G?, for 1 and 2 were determined to be 13.3¿0.3 kcal/mol and 16.3¿0.3 kcal/mol, respectively. This barrier is largely independent of solvent across those surveyed (CD3OD, CD3CN, DMSO-d6, pyridine-d5, D2O). Experiment and computation predict energy barriers that are consistent with disruption of an intramolecular network of hydrogen bonds. DFT calculations reveal a pathway for hinge motion. ¿ 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.
dc.languageen
dc.publisherJohn Wiley and Sons Inc
dc.sourceChemistry - A European Journal
dc.subjectcomputation
dc.subjecthinge
dc.subjectmacrocycle
dc.subjecttriazine
dc.subjectvariable temperature NMR
dc.titleControlling Swing Rates in Macrocyclic Molecular Mortise Hinges
dc.typeArticle
dc.rights.licenseCC BY 4.0
local.collegeCollege of Science and Engineering
local.departmentChemistry and Biochemistry
local.personsMenke, Mellberg, Janesko, Simanek (CHEM)


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