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Electronic and Magnetic Properties of Chiral Molecules and Supramolecular Architectures pp 99–128Cite as

Recent Theoretical and Experimental Advances in the Electronic Circular Dichroisms of Planar Chiral Cyclophanes

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Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 298))

Abstract

The chiroptical properties, such as electronic and vibrational circular dichroism and optical rotation, of planar chiral cyclophanes have attracted much attention in recent years. Although the chemistry of cyclophanes has been extensively explored for more than 60 years, the studies on chiral cyclophanes are rather limited. Experimentally, the use of chiral stationary phases in HPLC becomes more popular and facilitates the enantiomer separation of chiral cyclophanes of interest. Almost all chiral cyclophanes can be readily separated, in analytical and preparative scales, most typically on a Daicel OD type column, which is based on cellulose tris(3,5-dimethylphenylcarbamate). The CD spectra of chiral cyclophanes are unique in their fairly large, significantly coupled Cotton effects observed in all the 1 B b, 1 L a, and 1 L b band regions. Theoretically, the time-dependent density functional theory, or TD-DFT, method becomes a cost-efficient, yet accurate, theoretical method to reproduce the electronic circular dichroisms and the absorption spectra of a variety of cyclophanes. The direct comparison of the experimental CD spectra with the theoretical ones readily leads to the unambiguous assignment of the absolute configuration of cyclophanes. In addition, the analysis of configuration interaction and molecular orbitals allows detailed interpretation of the electronic transitions and Cotton effects in the UV and CD spectra. Through the study of the CD spectra of chiral cyclophanes as model systems, the effects of intra- and intermolecular interactions on the chiroptical properties of molecules can be explored, and the results thus obtained are valuable in comprehensively elucidating the structure-chiroptical property relationship. In this review the recent progress in experimental and theoretical investigations of the electronic CD spectra of chiral cyclophanes is discussed.

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Acknowledgments

T.M. thanks the Alexander von Humboldt-Stiftung for the fellowship. We thank Prof. Stefan Grimme at Universität Münster for his support at the very beginning of the calculations of CD spectra and fruitful discussion on the theoretical aspects. T.M. offers his thanks for the financial supports of this work by a Grant-in-Aid for Scientific Research (No. 21750044) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan, Mitsubishi Chemical Corporation Fund, and the Sumitomo Foundation. Y.I. offers his thanks for the support of this work by a Grant-in-Aid for Scientific Research (A) from JSPS (No. 21245011).

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

    Tadashi Mori & Yoshihisa Inoue

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  1. Tadashi Mori
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  2. Yoshihisa Inoue
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Correspondence to Tadashi Mori .

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  1. Dept. Chemical Physics, Weizmann Institute of Science, Rehovot, Israel

    Ron Naaman

  2. Duke University, Fitzpatrick Institute for Photonics, 101 Science Drive, Durham, NC, 27708, USA

    David N Beratan

  3. Chevron Science Center, Department of Chemistry, University of Pittsburgh, Parkman Avenue 219, Pittsburgh, 15260, Pennsylvania, USA

    David Waldeck

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Mori, T., Inoue, Y. (2010). Recent Theoretical and Experimental Advances in the Electronic Circular Dichroisms of Planar Chiral Cyclophanes. In: Naaman, R., Beratan, D., Waldeck, D. (eds) Electronic and Magnetic Properties of Chiral Molecules and Supramolecular Architectures. Topics in Current Chemistry, vol 298. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_2010_59

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