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Article: Photoactive azobenzene-containing supramolecular complexes and related interlocked molecular compounds

TitlePhotoactive azobenzene-containing supramolecular complexes and related interlocked molecular compounds
Authors
KeywordsCatenanes
Molecular devices
Molecular recognition
Rotaxanes
Template synthesis
Issue Date1999
Citation
Chemistry - A European Journal, 1999, v. 5, n. 3, p. 860-875 How to Cite?
AbstractTwo acyclic and three macrocyclic polyethers, three [2]catenanes, and one [2]rotaxane, each containing one 4,4′-azobiphenoxy unit, have been synthesized. In solution, the azobenzene-based acyclic polyethers are bound by cyclobis(paraquat-p-phenylene) - a tetracationic cyclophane - in their trans forms only. On irradiation (λ = 360 nm) of an equimolar solution of the tetracationic cyclophane host and one of the guests containing a trans-4,4′-azobiphenoxy unit, the trans double bond isomerizes to its cis form and the supramolecular complex dissociates into its molecular components. The trans isomer of the guest and, as a result, the complex are reformed, either by irradiation (λ = 440 nm) or by warming the solution in the dark. Variable temperature 1H NMR spectroscopic investigations of the [2]catenanes and the [2]rotaxane revealed that, in all cases, the 4,4′-azobiphenoxy unit resides preferentially alongside the cavities of their tetracationic cyclophane components, which are occupied either by a 1,4-dioxybenzene or by a 1,5-dioxynaphthalene unit. In the acyclic and macrocyclic polyethers containing 1,4-dioxybenzene or 1,5-dioxynaphthalene chromophoric groups and a 4,4′-azobiphenoxy moiety, the fluorescence of the former units is quenched by the latter. Fluorescence quenching is accompanied by photosensitization of the isomerization. The rate of the energy-transfer process is different for trans and cis isomers. In the [2]rotaxane and the [2]catenanes, the photoisomerization is quenched to an extent that depends on the specific structure of the compound. Only in one of the three [2]catenanes and in the [2]rotaxane was an efficient photoisomerization (λ = 360 nm) from the trans to the cis isomer of the 4,4′-azobiphenoxy unit observed. Single crystal X-ray structural analysis of one of the [2]catenanes showed that, in the solid state, the 4,4′-azobiphenoxy unit in the macrocyclic polyether component also resides exclusively alongside. The cavity of the tetracationic cyclophane component of the [2]catenane is filled by a 1,5-dioxynaphthalene unit, and infinite donor-acceptor stacks between adjacent [2]catenanes are formed in the crystal. These supramolecular complexes and their mechanically interlocked molecular counterparts can be regarded as potential photoactive nanoscale devices.
Persistent Identifierhttp://hdl.handle.net/10722/332450
ISSN
2023 Impact Factor: 3.9
2023 SCImago Journal Rankings: 1.058
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorAsakawa, Masumi-
dc.contributor.authorAshton, Peter R.-
dc.contributor.authorBalzani, Vincenzo-
dc.contributor.authorBrown, Christopher L.-
dc.contributor.authorCredi, Alberto-
dc.contributor.authorMatthews, Owen A.-
dc.contributor.authorNewton, Simon P.-
dc.contributor.authorRaymo, Françisco M.-
dc.contributor.authorShipway, Andrew N.-
dc.contributor.authorSpencer, Neil-
dc.contributor.authorQuick, Andrew-
dc.contributor.authorStoddart, J. Fraser-
dc.contributor.authorWhite, Andrew J.P.-
dc.contributor.authorWilliams, David J.-
dc.date.accessioned2023-10-06T05:11:36Z-
dc.date.available2023-10-06T05:11:36Z-
dc.date.issued1999-
dc.identifier.citationChemistry - A European Journal, 1999, v. 5, n. 3, p. 860-875-
dc.identifier.issn0947-6539-
dc.identifier.urihttp://hdl.handle.net/10722/332450-
dc.description.abstractTwo acyclic and three macrocyclic polyethers, three [2]catenanes, and one [2]rotaxane, each containing one 4,4′-azobiphenoxy unit, have been synthesized. In solution, the azobenzene-based acyclic polyethers are bound by cyclobis(paraquat-p-phenylene) - a tetracationic cyclophane - in their trans forms only. On irradiation (λ = 360 nm) of an equimolar solution of the tetracationic cyclophane host and one of the guests containing a trans-4,4′-azobiphenoxy unit, the trans double bond isomerizes to its cis form and the supramolecular complex dissociates into its molecular components. The trans isomer of the guest and, as a result, the complex are reformed, either by irradiation (λ = 440 nm) or by warming the solution in the dark. Variable temperature 1H NMR spectroscopic investigations of the [2]catenanes and the [2]rotaxane revealed that, in all cases, the 4,4′-azobiphenoxy unit resides preferentially alongside the cavities of their tetracationic cyclophane components, which are occupied either by a 1,4-dioxybenzene or by a 1,5-dioxynaphthalene unit. In the acyclic and macrocyclic polyethers containing 1,4-dioxybenzene or 1,5-dioxynaphthalene chromophoric groups and a 4,4′-azobiphenoxy moiety, the fluorescence of the former units is quenched by the latter. Fluorescence quenching is accompanied by photosensitization of the isomerization. The rate of the energy-transfer process is different for trans and cis isomers. In the [2]rotaxane and the [2]catenanes, the photoisomerization is quenched to an extent that depends on the specific structure of the compound. Only in one of the three [2]catenanes and in the [2]rotaxane was an efficient photoisomerization (λ = 360 nm) from the trans to the cis isomer of the 4,4′-azobiphenoxy unit observed. Single crystal X-ray structural analysis of one of the [2]catenanes showed that, in the solid state, the 4,4′-azobiphenoxy unit in the macrocyclic polyether component also resides exclusively alongside. The cavity of the tetracationic cyclophane component of the [2]catenane is filled by a 1,5-dioxynaphthalene unit, and infinite donor-acceptor stacks between adjacent [2]catenanes are formed in the crystal. These supramolecular complexes and their mechanically interlocked molecular counterparts can be regarded as potential photoactive nanoscale devices.-
dc.languageeng-
dc.relation.ispartofChemistry - A European Journal-
dc.subjectCatenanes-
dc.subjectMolecular devices-
dc.subjectMolecular recognition-
dc.subjectRotaxanes-
dc.subjectTemplate synthesis-
dc.titlePhotoactive azobenzene-containing supramolecular complexes and related interlocked molecular compounds-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/(SICI)1521-3765(19990301)5:3<860::AID-CHEM860>3.0.CO;2-K-
dc.identifier.scopuseid_2-s2.0-0033064484-
dc.identifier.volume5-
dc.identifier.issue3-
dc.identifier.spage860-
dc.identifier.epage875-
dc.identifier.isiWOS:000079224400005-

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