Stereospecific Winding of Polycyclic Aromatic Hydrocarbons into Trinacria Propellers

Research output: Contribution to journalArticle

Abstract

The stereospecific trimerization of enantiomerically pure binaphthols with hexakis(bromomethyl)benzene gives access in one step to enantiomerically pure molecular propellers, in which three binaphthyl rings are held together with dioxecine rings. X-ray diffraction analysis revealed that three out the six naphthyl moieties are folded in a (EF)3 -type arrangement held by three intramolecular C-H⋅⋅⋅π interactions. This slips outward the three remaining naphthyl rings in a blade-like fashion, just like in three-folded propeller components. This peculiar conformation shows striking similarity to the mythological Sicilian symbol of Trinacria, from which the name "trinacria propeller" derives. The propeller conformation is also preserved in chlorinated solutions, as displayed by the presence of a peak at 4.7 ppm typical of an aromatic proton resonance engaged in a C-H⋅⋅⋅π interaction. The denaturation of the propeller-like conformation is obtained at high temperature, corresponding to activation energy for the ring inversion of ca. 18.2 kcal mol-1 . Notably, halide-functionalized molecular propellers exposing I-atoms at the leading and trailing edges could be prepared stereo- and regiospecifically by choosing the relevant iodo-bearing BINOL derivative.

Original languageEnglish
Pages (from-to)15348-15354
Number of pages7
JournalChemistry - A European Journal
Volume23
Issue number61
DOIs
Publication statusPublished - 2 Nov 2017
Externally publishedYes

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Polycyclic Aromatic Hydrocarbons
Propellers
Polycyclic aromatic hydrocarbons
Conformations
Bearings (structural)
Denaturation
Benzene
X ray diffraction analysis
Protons
Activation energy
Derivatives
Atoms
Hydrogen

Keywords

  • Journal Article
  • molecular propellers
  • chirality
  • aromatic embrace
  • molecular motors
  • polycycles

Cite this

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abstract = "The stereospecific trimerization of enantiomerically pure binaphthols with hexakis(bromomethyl)benzene gives access in one step to enantiomerically pure molecular propellers, in which three binaphthyl rings are held together with dioxecine rings. X-ray diffraction analysis revealed that three out the six naphthyl moieties are folded in a (EF)3 -type arrangement held by three intramolecular C-H⋅⋅⋅π interactions. This slips outward the three remaining naphthyl rings in a blade-like fashion, just like in three-folded propeller components. This peculiar conformation shows striking similarity to the mythological Sicilian symbol of Trinacria, from which the name {"}trinacria propeller{"} derives. The propeller conformation is also preserved in chlorinated solutions, as displayed by the presence of a peak at 4.7 ppm typical of an aromatic proton resonance engaged in a C-H⋅⋅⋅π interaction. The denaturation of the propeller-like conformation is obtained at high temperature, corresponding to activation energy for the ring inversion of ca. 18.2 kcal mol-1 . Notably, halide-functionalized molecular propellers exposing I-atoms at the leading and trailing edges could be prepared stereo- and regiospecifically by choosing the relevant iodo-bearing BINOL derivative.",
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author = "Dario Mosca and Antoine Stopin and Johan Wouters and Nicola Demitri and Davide Bonifazi",
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Stereospecific Winding of Polycyclic Aromatic Hydrocarbons into Trinacria Propellers. / Mosca, Dario; Stopin, Antoine; Wouters, Johan; Demitri, Nicola; Bonifazi, Davide.

In: Chemistry - A European Journal, Vol. 23, No. 61, 02.11.2017, p. 15348-15354.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Stereospecific Winding of Polycyclic Aromatic Hydrocarbons into Trinacria Propellers

AU - Mosca, Dario

AU - Stopin, Antoine

AU - Wouters, Johan

AU - Demitri, Nicola

AU - Bonifazi, Davide

N1 - © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

PY - 2017/11/2

Y1 - 2017/11/2

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KW - molecular motors

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