1 Ocak 2019 Dergi makalesi Açık Erişim

Pavlovic, Radoslav Z.; Lei Zhiquan; Guney, Murat; Lalisse, Remy F.; Hopf, Ryan G.; Gallucci, Judith; Moore, Curtis; Xie, Han; Hadad, Christopher M.; Badjic, Jovica D.

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  <identifier identifierType="URL">https://aperta.ulakbim.gov.tr/record/72453</identifier>
  <creators>
    <creator>
      <creatorName>Pavlovic, Radoslav Z.</creatorName>
      <givenName>Radoslav Z.</givenName>
      <familyName>Pavlovic</familyName>
      <affiliation>Ohio State Univ, Dept Chem &amp; Biochem, 100 West 18th Ave, Columbus, OH 43210 USA</affiliation>
    </creator>
    <creator>
      <creatorName>Lei Zhiquan</creatorName>
      <affiliation>Ohio State Univ, Dept Chem &amp; Biochem, 100 West 18th Ave, Columbus, OH 43210 USA</affiliation>
    </creator>
    <creator>
      <creatorName>Guney, Murat</creatorName>
      <givenName>Murat</givenName>
      <familyName>Guney</familyName>
      <affiliation>Ibrahim Cecen Univ Agri, Dept Chem, Sci &amp; Art Fac, Agri, Turkey</affiliation>
    </creator>
    <creator>
      <creatorName>Lalisse, Remy F.</creatorName>
      <givenName>Remy F.</givenName>
      <familyName>Lalisse</familyName>
      <affiliation>Ohio State Univ, Dept Chem &amp; Biochem, 100 West 18th Ave, Columbus, OH 43210 USA</affiliation>
    </creator>
    <creator>
      <creatorName>Hopf, Ryan G.</creatorName>
      <givenName>Ryan G.</givenName>
      <familyName>Hopf</familyName>
      <affiliation>Ohio State Univ, Dept Chem &amp; Biochem, 100 West 18th Ave, Columbus, OH 43210 USA</affiliation>
    </creator>
    <creator>
      <creatorName>Gallucci, Judith</creatorName>
      <givenName>Judith</givenName>
      <familyName>Gallucci</familyName>
      <affiliation>Ohio State Univ, Dept Chem &amp; Biochem, 100 West 18th Ave, Columbus, OH 43210 USA</affiliation>
    </creator>
    <creator>
      <creatorName>Moore, Curtis</creatorName>
      <givenName>Curtis</givenName>
      <familyName>Moore</familyName>
      <affiliation>Ohio State Univ, Dept Chem &amp; Biochem, 100 West 18th Ave, Columbus, OH 43210 USA</affiliation>
    </creator>
    <creator>
      <creatorName>Xie, Han</creatorName>
      <givenName>Han</givenName>
      <familyName>Xie</familyName>
      <affiliation>Ohio State Univ, Dept Chem &amp; Biochem, 100 West 18th Ave, Columbus, OH 43210 USA</affiliation>
    </creator>
    <creator>
      <creatorName>Hadad, Christopher M.</creatorName>
      <givenName>Christopher M.</givenName>
      <familyName>Hadad</familyName>
      <affiliation>Ohio State Univ, Dept Chem &amp; Biochem, 100 West 18th Ave, Columbus, OH 43210 USA</affiliation>
    </creator>
    <creator>
      <creatorName>Badjic, Jovica D.</creatorName>
      <givenName>Jovica D.</givenName>
      <familyName>Badjic</familyName>
      <affiliation>Ohio State Univ, Dept Chem &amp; Biochem, 100 West 18th Ave, Columbus, OH 43210 USA</affiliation>
    </creator>
  </creators>
  <titles>
    <title>Multivalent C-H...Cl/Br-C Interactions Directing The Resolution Of Dynamic And Twisted Capsules</title>
  </titles>
  <publisher>Aperta</publisher>
  <publicationYear>2019</publicationYear>
  <dates>
    <date dateType="Issued">2019-01-01</date>
  </dates>
  <resourceType resourceTypeGeneral="Text">Journal article</resourceType>
  <alternateIdentifiers>
    <alternateIdentifier alternateIdentifierType="url">https://aperta.ulakbim.gov.tr/record/72453</alternateIdentifier>
  </alternateIdentifiers>
  <relatedIdentifiers>
    <relatedIdentifier relatedIdentifierType="DOI" relationType="IsIdenticalTo">10.1002/chem.201903006</relatedIdentifier>
  </relatedIdentifiers>
  <rightsList>
    <rights rightsURI="http://www.opendefinition.org/licenses/cc-by">Creative Commons Attribution</rights>
    <rights rightsURI="info:eu-repo/semantics/openAccess">Open Access</rights>
  </rightsList>
  <descriptions>
    <description descriptionType="Abstract">In this work, we report a mechanism by which stereoisomeric and twisted capsules P/M-1 direct their dynamic chirality in the presence of haloalkane guests. The capsule comprises a static, but twisted, cage that is linked to a dynamic tris(2-pyridylmethyl)amine (TPA) lid at its top. From the results of experimental (NMR spectroscopy and X-ray crystallography) and computational (DFT) studies, the TPA lid was shown to assume clockwise (+) and counterclockwise (-) folds with diastereomeric (but racemic) capsules M-1(+) and M-1(-) interconverting at a rapid rate (Delta G(189K)(not equal)=9.1 kcal mol(-1)). The relative stability of the capsules was found to be a function of guest(s) residing in their interior (243/262 angstrom(3)) with small CH2Cl2 (61 angstrom(3)) yielding roughly equal population of diastereomeric inclusion complexes. Larger guests, such as CCl4 (89 angstrom(3)) and CBr4 (108 angstrom(3)), however, formed M-1(-)subset of CX4 at the expense of M-1(+)subset of CX4 in circa 3:1 ratio. To account for the observation, theory (DFT:M06-2X/6-31+G*) and experiments (H-1 NMR spectroscopy) were used to deduce that CX4 guests become localized inside the twisted cage of the capsule by forming a C-X...pi halogen bond [N-c=d/(r(H)+r(X))=0.91-0.92] with the benzene "floor" while encountering electrostatic repulsions with closer naphthalimide boundaries. At last, the TPA lid used its central methylene hydrogens to establish, within the M-1(-)subset of CX4, three stabilizing C-H...X-C interactions with the guest. The same C-H...X-C interactions, however, became weaker (or possibly vanished) after the conformational reorganization of the lid and the formation of less stable M-1(+)subset of CX4 complex. On individual basis, C-H...X-C intermolecular contacts are weak and hardly detectable in the solution phase. In the case of capsule P/M-1, however, these contacts were multivalent and altogether strong enough to direct the host's dynamic chirality.</description>
  </descriptions>
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