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Article: Structure-reactivity relationship in interlocked molecular compounds and in their supramolecular model complexes
Title | Structure-reactivity relationship in interlocked molecular compounds and in their supramolecular model complexes |
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Authors | |
Issue Date | 1997 |
Citation | Journal of the American Chemical Society, 1997, v. 119, n. 11, p. 2614-2627 How to Cite? |
Abstract | Examination 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 Identifier | http://hdl.handle.net/10722/332408 |
ISSN | 2023 Impact Factor: 14.4 2023 SCImago Journal Rankings: 5.489 |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Asakawa, Masumi | - |
dc.contributor.author | Brown, Christopher L. | - |
dc.contributor.author | Menzer, Stephan | - |
dc.contributor.author | Raymo, Françisco M. | - |
dc.contributor.author | Stoddart, J. Fraser | - |
dc.contributor.author | Williams, David J. | - |
dc.date.accessioned | 2023-10-06T05:11:15Z | - |
dc.date.available | 2023-10-06T05:11:15Z | - |
dc.date.issued | 1997 | - |
dc.identifier.citation | Journal of the American Chemical Society, 1997, v. 119, n. 11, p. 2614-2627 | - |
dc.identifier.issn | 0002-7863 | - |
dc.identifier.uri | http://hdl.handle.net/10722/332408 | - |
dc.description.abstract | Examination 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.language | eng | - |
dc.relation.ispartof | Journal of the American Chemical Society | - |
dc.title | Structure-reactivity relationship in interlocked molecular compounds and in their supramolecular model complexes | - |
dc.type | Article | - |
dc.description.nature | link_to_subscribed_fulltext | - |
dc.identifier.doi | 10.1021/ja962937z | - |
dc.identifier.scopus | eid_2-s2.0-0030972332 | - |
dc.identifier.volume | 119 | - |
dc.identifier.issue | 11 | - |
dc.identifier.spage | 2614 | - |
dc.identifier.epage | 2627 | - |
dc.identifier.isi | WOS:A1997WN85500003 | - |