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

Gaku Fukuhara, Frank Gerrit Klärner, Tadashi Mori, Takehiko Wada, Yoshihisa Inoue

Research output: Contribution to journalArticlepeer-review

10 Citations (Scopus)

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 (ΔH° = -96.4 kJ mol-1, ΔS° = -239 J mol -1 K-1) reveal that the binding of DPP by MC is strongly driven by the enthalpic gain from hydrophobic and π-π 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.

Original languageEnglish
Pages (from-to)1493-1500
Number of pages8
JournalPhotochemical and Photobiological Sciences
Volume7
Issue number12
DOIs
Publication statusPublished - 2008

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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