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Article: Structure-reactivity relationship in interlocked molecular compounds and in their supramolecular model complexes

TitleStructure-reactivity relationship in interlocked molecular compounds and in their supramolecular model complexes
Authors
Issue Date1997
Citation
Journal of the American Chemical Society, 1997, v. 119, n. 11, p. 2614-2627 How to Cite?
AbstractExamination of the pseudorotaxane-like geometries adopted in the solid state by a series of 1:1 complexes revealed significant differences in the hydrogen bonding interactions between oxygen atoms in some hydroquinone-based guests carrying polyether/polyester functions and the acidic hydrogen atoms on the bipyridinium units of the host-cyclobis(paraquat-p-phenylene). These differences are reflected directly in the stabilities of the complexes in solution and dramatic changes in the magnitudes of their association constants (K(a) values ranging from 130 to 4300 M-1 in MeCN at 25 °C) are observed upon varying the location of the carbonyl ester function(s) along the polyether/ester chains. A similar effect (K(a) values ranging from 5 to 730 M-1 in Me2CO at 25 °C) was observed in the binding of paraquat as its bipyridinium bis(hexafluorophosphate) salt by analogous macrocyclic hydroquinone-based mono- and bis-lactones. Investigations of the kinetics of hydrolyses of the ester functions revealed that-while inert in their free forms-the macrocyclic mono- and bis-lactones undergo hydrolysis when incorporated within catenanes composed of one of these macrocyclic lactones and cyclobis(paraquat-p-phenylene). Presumably, the enhanced reactivity of the ester functions is a result of [C-H...O] hydrogen bonding interactions involving the ester carbonyl oxygen atoms and the acidic hydrogen atoms on the bipyridinium units, as suggested by single-crystal X-ray crystallographic analyses. Thus, cyclobis(paraquat-p-phenylene) can act as a mechanically-interlocked 'catalyst'.
Persistent Identifierhttp://hdl.handle.net/10722/332408
ISSN
2023 Impact Factor: 14.4
2023 SCImago Journal Rankings: 5.489
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorAsakawa, Masumi-
dc.contributor.authorBrown, Christopher L.-
dc.contributor.authorMenzer, Stephan-
dc.contributor.authorRaymo, Françisco M.-
dc.contributor.authorStoddart, J. Fraser-
dc.contributor.authorWilliams, David J.-
dc.date.accessioned2023-10-06T05:11:15Z-
dc.date.available2023-10-06T05:11:15Z-
dc.date.issued1997-
dc.identifier.citationJournal of the American Chemical Society, 1997, v. 119, n. 11, p. 2614-2627-
dc.identifier.issn0002-7863-
dc.identifier.urihttp://hdl.handle.net/10722/332408-
dc.description.abstractExamination of the pseudorotaxane-like geometries adopted in the solid state by a series of 1:1 complexes revealed significant differences in the hydrogen bonding interactions between oxygen atoms in some hydroquinone-based guests carrying polyether/polyester functions and the acidic hydrogen atoms on the bipyridinium units of the host-cyclobis(paraquat-p-phenylene). These differences are reflected directly in the stabilities of the complexes in solution and dramatic changes in the magnitudes of their association constants (K(a) values ranging from 130 to 4300 M-1 in MeCN at 25 °C) are observed upon varying the location of the carbonyl ester function(s) along the polyether/ester chains. A similar effect (K(a) values ranging from 5 to 730 M-1 in Me2CO at 25 °C) was observed in the binding of paraquat as its bipyridinium bis(hexafluorophosphate) salt by analogous macrocyclic hydroquinone-based mono- and bis-lactones. Investigations of the kinetics of hydrolyses of the ester functions revealed that-while inert in their free forms-the macrocyclic mono- and bis-lactones undergo hydrolysis when incorporated within catenanes composed of one of these macrocyclic lactones and cyclobis(paraquat-p-phenylene). Presumably, the enhanced reactivity of the ester functions is a result of [C-H...O] hydrogen bonding interactions involving the ester carbonyl oxygen atoms and the acidic hydrogen atoms on the bipyridinium units, as suggested by single-crystal X-ray crystallographic analyses. Thus, cyclobis(paraquat-p-phenylene) can act as a mechanically-interlocked 'catalyst'.-
dc.languageeng-
dc.relation.ispartofJournal of the American Chemical Society-
dc.titleStructure-reactivity relationship in interlocked molecular compounds and in their supramolecular model complexes-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/ja962937z-
dc.identifier.scopuseid_2-s2.0-0030972332-
dc.identifier.volume119-
dc.identifier.issue11-
dc.identifier.spage2614-
dc.identifier.epage2627-
dc.identifier.isiWOS:A1997WN85500003-

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