File Download

There are no files associated with this item.

  Links for fulltext
     (May Require Subscription)
Supplementary

Article: Donor-acceptor ring-in-ring complexes

TitleDonor-acceptor ring-in-ring complexes
Authors
Keywordsdonor-acceptor systems
host-guest systems
self-assembly
template synthesis
X-ray diffraction
Issue Date2012
Citation
Chemistry - A European Journal, 2012, v. 18, n. 1, p. 202-212 How to Cite?
AbstractThe self-assembly of three donor-acceptor ring-in-ring complexes, prepared from the π-electron-deficient tetracationic cyclophane, cyclobis(paraquat-4, 4′-biphenylene), and three large π-electron-rich crown ethers (each 50-membered rings) containing dioxynaphthalene (DNP) and tetrathiafulvalene (TTF) units in pairs (DNP/DNP, DNP/TTF and TTF/TTF), is reported. 1HNMR spectroscopic analyses are indicative of the formation of 1:1 complexes in CD 3CN, whilst the charge-transfer interactions between the DNP and TTF units of the crown ethers and the tetracationic cyclophane have permitted the measurement of binding constants of up to 4 × 10 3M -1 in CH 3CN to be made using UV/Vis spectroscopy. Ring-in-ring complexes are proposed as intermediates in the stepwise synthesis of molecular Borromean rings (BRs) comprised of three different rings. With the particular choice of crown ethers, the 1:1 complexes have polyether loops that protrude from the donor-acceptor recognition point above and below the mean plane of the tetracationic cyclophane, which, ideally, could conceivably bind dialkylammonium centers present in a third ring. X-ray crystallographic analyses of the solid-state superstructures of two of the three 1:1 complexes reveal, however, the presence of prodigious CH̄O interactions between the polyether loops of the crown ethers and the rims of the cyclophane, no doubt stabilizing the complexes, but, at the same time, masking their potential recognition sites from further interactions that are essential to the subsequent emergence of the third ring. The solid-state superstructure of one of the crown ethers binding two dibenzylammonium ions provides some insight into the design requirements for the next generation of these systems; longer polyether loops may be required to allow optimal interactions between all components. It has become clear during a pursuit of the stepwise synthesis of the molecular BRs that, when designing complex mechanically interlocked molecules utilizing multiple recognition sites, the unsullied orthogonality of the recognition motifs is of the utmost importance. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Persistent Identifierhttp://hdl.handle.net/10722/333621
ISSN
2023 Impact Factor: 3.9
2023 SCImago Journal Rankings: 1.058
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorForgan, Ross S.-
dc.contributor.authorWang, Cheng-
dc.contributor.authorFriedman, Douglas C.-
dc.contributor.authorSpruell, Jason M.-
dc.contributor.authorStern, Charlotte L.-
dc.contributor.authorSarjeant, Amy A.-
dc.contributor.authorCao, Dennis-
dc.contributor.authorStoddart, J. Fraser-
dc.date.accessioned2023-10-06T05:21:05Z-
dc.date.available2023-10-06T05:21:05Z-
dc.date.issued2012-
dc.identifier.citationChemistry - A European Journal, 2012, v. 18, n. 1, p. 202-212-
dc.identifier.issn0947-6539-
dc.identifier.urihttp://hdl.handle.net/10722/333621-
dc.description.abstractThe self-assembly of three donor-acceptor ring-in-ring complexes, prepared from the π-electron-deficient tetracationic cyclophane, cyclobis(paraquat-4, 4′-biphenylene), and three large π-electron-rich crown ethers (each 50-membered rings) containing dioxynaphthalene (DNP) and tetrathiafulvalene (TTF) units in pairs (DNP/DNP, DNP/TTF and TTF/TTF), is reported. 1HNMR spectroscopic analyses are indicative of the formation of 1:1 complexes in CD 3CN, whilst the charge-transfer interactions between the DNP and TTF units of the crown ethers and the tetracationic cyclophane have permitted the measurement of binding constants of up to 4 × 10 3M -1 in CH 3CN to be made using UV/Vis spectroscopy. Ring-in-ring complexes are proposed as intermediates in the stepwise synthesis of molecular Borromean rings (BRs) comprised of three different rings. With the particular choice of crown ethers, the 1:1 complexes have polyether loops that protrude from the donor-acceptor recognition point above and below the mean plane of the tetracationic cyclophane, which, ideally, could conceivably bind dialkylammonium centers present in a third ring. X-ray crystallographic analyses of the solid-state superstructures of two of the three 1:1 complexes reveal, however, the presence of prodigious CH̄O interactions between the polyether loops of the crown ethers and the rims of the cyclophane, no doubt stabilizing the complexes, but, at the same time, masking their potential recognition sites from further interactions that are essential to the subsequent emergence of the third ring. The solid-state superstructure of one of the crown ethers binding two dibenzylammonium ions provides some insight into the design requirements for the next generation of these systems; longer polyether loops may be required to allow optimal interactions between all components. It has become clear during a pursuit of the stepwise synthesis of the molecular BRs that, when designing complex mechanically interlocked molecules utilizing multiple recognition sites, the unsullied orthogonality of the recognition motifs is of the utmost importance. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.-
dc.languageeng-
dc.relation.ispartofChemistry - A European Journal-
dc.subjectdonor-acceptor systems-
dc.subjecthost-guest systems-
dc.subjectself-assembly-
dc.subjecttemplate synthesis-
dc.subjectX-ray diffraction-
dc.titleDonor-acceptor ring-in-ring complexes-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/chem.201102919-
dc.identifier.scopuseid_2-s2.0-84555190094-
dc.identifier.volume18-
dc.identifier.issue1-
dc.identifier.spage202-
dc.identifier.epage212-
dc.identifier.eissn1521-3765-
dc.identifier.isiWOS:000298547800026-

Export via OAI-PMH Interface in XML Formats


OR


Export to Other Non-XML Formats