Computational NMR spectra of o-benzyne and stable guests and their hemicarceplexes
dc.contributor.author
dc.date.accessioned
2019-12-17T08:29:17Z
dc.date.available
2019-12-17T08:29:17Z
dc.date.issued
2019-11-25
dc.identifier.issn
0947-6539
dc.identifier.uri
dc.description.abstract
The incarceration of o‐benzyne and 27 other guest molecules within hemicarcerand 1, as reported experimentally by Warmuth, and Cram and co‐workers, respectively, has been studied by density functional theory (DFT). 1H‐NMR chemical shifts, rotational mobility and conformational preference of the guests within the supramolecular cage were determined, which showed intriguing correlations of the chemical shifts with structural parameters of the host‐guest system. Furthermore, based on the computed chemical shifts reassignments of some NMR signals are proposed. This affects in particular the putative characterization of the volatile benzyne molecule inside a hemicarcerand, for which our CCSD(T) and KT2 results indicate that the experimentally observed signals are most likely not resulting from an isolated benzyne within the supramolecular host. Instead, we show that the guest reacted with an aromatic ring of the host, and this adduct is responsible for the experimentally observed signals
dc.description.sponsorship
The following organizations are thanked for financial support: MICINN (PhD-scholarship ACC CTQ2011-25086/BQU, projects CTQ2014-59212-P, CTQ2015-70851-ERC, CTQ2017-87392-P), CONACyT project 2014-383560, GenCat (PhD scholarship ARR 2015_FI_B_00165, 2014SGR1202 and XRQTC network) and European Fund for Regional Development (FEDER, UNGI10-4E-801)
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Wiley
dc.relation
info:eu-repo/grantAgreement/MICINN//CTQ2011-25086/ES/MODELIZACION MULTIESCALAR EN (BIO)QUIMICA/
info:eu-repo/grantAgreement/MINECO//CTQ2014-59212-P/ES/SPIN STATE AND ENZYMATIC CATALYSIS BASED ON BOTTOM-UP COMPUTATIONAL DESIGN/
info:eu-repo/grantAgreement/MINECO//CTQ2015-70851-ERC/ES/SPIN STATE CATALYSIS THROUGH DENSITY-CONSISTENT MOLECULAR MODELLING/
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-87392-P/ES/CHARACTERIZATION AND PREDICTION OF SHORT-LIVED TRANSITION-METAL SPECIES/
dc.relation.isformatof
Versió postprint del document publicat a: https://doi.org/10.1002/chem.201904756
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© Chemistry-A European Journal, 2019, vol.undef, núm undef, p. undef
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Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.subject
dc.title
Computational NMR spectra of o-benzyne and stable guests and their hemicarceplexes
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2020-11-25
dc.type.version
info:eu-repo/semantics/acceptedVersion
dc.identifier.doi
dc.identifier.idgrec
028428
dc.contributor.funder
dc.type.peerreviewed
peer-reviewed
dc.relation.FundingProgramme
dc.relation.ProjectAcronym
dc.identifier.eissn
1521-3765