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Supramolecular complexation and photochirogenesis with inherently chiral molecular clip: enantiodifferentiating photoisomerization of (Z,Z)-1,3-cyclooctadiene and polar photoaddition to 1,1-diphenylpropene

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Abstract

Inherently chiral molecular clip (MC) 2 binds (Z,Z)-1,3-cyclooctadiene (COD) and 1,1-diphenylpropene (DPP) in 4:1:5 THF-MeOH-H2O solution (at 25 °C) with association constants of 8800 and 27000 M-1, respectively. The thermodynamic parameters obtained from the van’t Hoff analysis (DH° = -96.4 kJ mol-1, DS° = -239 J mol-1 K-1) reveal that the binding of DPP by MC is strongly driven by the enthalpic gain from hydrophobic and p-p stacking interactions, which is however largely cancelled out by the entropic loss arising from the tight molecular association. Supramolecular photosensitization by MC 2 facilitates the Z-E isomerization of COD to chiral (E,Z)-isomer in a good E/Z ratio of 0.19 and a low ee of 0.7%, but does not appear to work with DPP probably due to the less-efficient electron transfer in the acceptor-donor-acceptor complex of DPP with MC 2.

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Author notes

  1. Takehiko Wada

    Present address: Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira, Aoba-ku, 980-8577, Sendai, Germany

Authors and Affiliations

  1. Department of Applied Chemistry, Osaka University, 2-1 Yamada-oka, Suita, 565-0871, Japan

    Gaku Fukuhara, Tadashi Mori, Takehiko Wada & Yoshihisa Inoue

  2. Institute of Organic Chemistry, University of Duisburg-Essen, 45117, Essen, Germany

    Frank-Gerrit Klärner

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  1. Gaku Fukuhara
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Correspondence to Frank-Gerrit Klärner or Yoshihisa Inoue.

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This paper was published as part of the themed issue in honour of Nicholas Turro.

Current address: Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira, Aoba-ku, Sendai, 980-8577, Japan.

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Fukuhara, G., Klärner, FG., Mori, T. et al. Supramolecular complexation and photochirogenesis with inherently chiral molecular clip: enantiodifferentiating photoisomerization of (Z,Z)-1,3-cyclooctadiene and polar photoaddition to 1,1-diphenylpropene. Photochem Photobiol Sci 7, 1493–1500 (2008). https://doi.org/10.1039/b812186a

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  • DOI: https://doi.org/10.1039/b812186a

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